Compositions and aggregates comprising boron nitride nanotube structures, and methods of making

ABSTRACT

A composition (or an aggregate) comprising a h-BN/BNNT structure that comprises a boron nitride nanotube structure and at least a first hexagonal boron nitride structure. Also, a composition comprising at least a first epitaxial h-BN/BNNT structure and at least one metal adhered to the first epitaxial h-BN/BNNT structure. Also, a composition (or an aggregate) that comprises independent boron nitride nanotubes, in which a total mass percentage of independent hexagonal boron nitride and residual boron in the composition is not more than 35%. Also, a material comprising at least a first hexagonal boron nitride structure and at least a first boron nitride nanotube structure, wherein atoms in the first hexagonal boron nitride structure are epitaxially aligned with atoms in the first boron nitride nanotube structure that are closest to the first hexagonal boron nitride structure.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/928,969, filed Mar. 22, 2018 now U.S. Pat. No. 11,332,369, theentirety of which is incorporated herein by reference.

FIELD OF THE INVENTIVE SUBJECT MATTER

The present inventive subject matter relates to novel and unforeseenmaterials that each comprise an arrangement of atoms that includes afirst region of the arrangement of atoms corresponding (to at least aspecified extent) to an idealized boron nitride nanotube, thearrangement of atoms also including at least a second region (thatdiffers from the first region), such novel and unforeseen materialshaving unique combinations of properties.

In one aspect of the present inventive subject matter, therefore, thepresent inventive subject matter provides novel and unforeseen materialsthat have unique combinations of properties.

The present inventive subject matter also provides novel compositionsand aggregates that include such novel and unforeseen materials.

The present inventive subject matter also provides novel compositionsand aggregates that comprise boron nitride nanotubes and that have novelcharacteristics.

The present inventive subject matter also provides novel methods ofmaking the novel and unforeseen materials, compositions and aggregates.

BACKGROUND

Boron nitride nanotubes are nano-scale hollow tubes, typically ofdiameters in the range of from 2 to 20 nanometers, and typically oflengths in the range of tens of nanometers up to tens of microns. Theexpression “boron nitride nanotube” (or “boron nitride nanotubes”)encompasses structures that consist of a single layer which is generallytubular (i.e., single-wall boron nitride nanotubes) as well asstructures that consist of multiple layers which are each generallytubular and coaxial (i.e., multi-wall boron nitride nanotubes).

A hypothetical idealized boron nitride nanotube consists of one or morelayers (i.e., walls), each layer consisting of a generally tubulararrangement of boron atoms and nitrogen atoms, the boron atoms andnitrogen atoms arranged in a repeating hexagonal pattern in which boronatoms and nitrogen atoms alternate. As is well known by persons of skillin the art, an idealized boron nitride nanotube can be conceptualized asthe structure that would result from taking a layer (or plural layers)of boron and nitrogen atoms, in which boron and nitrogen are arrangedalternatingly in a repeating hexagonal pattern, curling the layer (orlayers) so that two sides of the layer (or respective layers) meet alonga seam and connect, with the seam matching the alternatingboron/nitrogen repeating hexagonal pattern, to provide a hollowcylindrical array of one wall (or of a number of walls corresponding tothe number of layers) of boron and nitrogen atoms in a continuousalternating hexagonal pattern (i.e., the seam is not discernable).

Boron nitride nanotubes are often compared with carbon nanotubes interms of their respective chemical structures and their respectiveproperties. It has been noted that while there are similarities (e.g.,excellent mechanical strength), there are also many differences,including (among many other differences) that boron nitride nanotubesare electrically insulating (whereas carbon nanotubes are electricallyconductive), and that boron nitride nanotubes are stable to much highertemperatures.

The many strikingly favorable properties of boron nitride nanotubesinclude, inter alia, strength-to-mass ratio (high strength/low density),toughness, stiffness, thermal conductance, flame resistance, corrosionresistance, neutron radiation absorption/protection, friction and wearresistance, oxidation resistance, hydrophobicity, hydrogen storagecapacity, nanoparticle carrier effectiveness, and other properties.

There are a number of forms of defective boron nitride nanotubes thatare well known to persons of skill in the art, e.g., dixie cup defectsand bamboo defects.

BRIEF SUMMARY OF THE INVENTIVE SUBJECT MATTER

As noted above, the present inventive subject matter provides, in oneaspect, novel and unforeseen materials (epitaxial h-BN/BNNT structures,as defined herein) that each comprise an arrangement of atoms thatincludes a first region of the arrangement of atoms corresponding (to atleast a specified extent) to an idealized boron nitride nanotube, thearrangement of atoms also including at least a second region (thatdiffers from the first region), such novel and unforeseen materialshaving unique combinations of properties.

In accordance with a first aspect of the present inventive subjectmatter, there is provided a composition comprising at least a firstepitaxial h-BN/BNNT structure (as defined herein), the first epitaxialh-BN/BNNT structure comprising at least a first boron nitride nanotubestructure (as also defined herein) and at least a first hexagonal boronnitride structure (as also defined herein), the first hexagonal boronnitride structure epitaxial with respect to the first boron nitridenanotube structure (as also defined herein).

In accordance with a second aspect of the present inventive subjectmatter, there is provided an aggregate that comprises a one-piecestructure comprising at least a first epitaxial h-BN/BNNT structure (asdefined herein), the first epitaxial h-BN/BNNT structure comprising atleast a first boron nitride nanotube structure (as also defined herein)and at least a first hexagonal boron nitride structure (as also definedherein), the first hexagonal boron nitride structure epitaxial withrespect to the boron nitride nanotube structure (as also definedherein), the one-piece structure having a first dimension of at least100 nm and a second dimension of at least 100 nm, the second dimensionperpendicular to the first dimension.

The present inventive subject matter also provides other novelcompositions and aggregates that comprise epitaxial h-BN/BNNT structuresas defined herein.

The novel and unforeseen epitaxial h-BN/BNNT structures (as definedherein) provided by the present inventive subject matter exhibitimproved properties, e.g., excellent adherence to matrix materials (suchas enhanced physical/mechanical resistance to removal from matrixmaterials), provide excellent nano-nucleation sites for metals tocrystallize (e.g., in the case of casting one or more metals, such asaluminum, magnesium, titanium, which have melting points that are lowerthan the temperature at which boron nitride nanotube structuresdegrade), and can provide favorable properties even after beingsubjected to extremely high temperatures.

The present inventive subject matter also provides novel compositionsand aggregates that comprise independent boron nitride nanotubes (asdefined herein) and that have novel characteristics.

The present inventive subject matter also relates to high-puritycompositions and aggregates that comprise boron nitride nanotubestructures and/or independent boron nitride nanotubes, e.g.,compositions and aggregates that comprise boron nitride nanotubestructures and/or independent boron nitride nanotubes and in which thecombined amount of residual boron and independent hexagonal boronnitride (as defined herein) is limited to being below (or not greaterthan) specific mass percentages.

In accordance with a third aspect of the present inventive subjectmatter, there is provided a composition that comprises a plurality ofindependent boron nitride nanotubes (as defined herein), in which a sumof [1] a total mass of any independent hexagonal boron nitride (as alsodefined herein) in the composition and [2] a total mass of any residualboron (as also defined herein) in the composition accounts for not morethan 35% of the mass of the composition.

In accordance with a fourth aspect of the present inventive subjectmatter, there is provided an aggregate that comprises a one-piecestructure comprising a plurality of independent boron nitride nanotubes(as defined herein), the one-piece structure having a first dimension ofat least 100 nm and a second dimension of at least 100 nm, the seconddimension perpendicular to the first dimension, a sum of [1] a totalmass of independent hexagonal boron nitride (as also defined herein) inthe one-piece structure and [2] a total mass of any residual boron (asalso defined herein) in the one-piece structure accounts for not morethan 35% of the mass of the one-piece structure.

The present inventive subject matter also relates to high-qualitycompositions and aggregates that comprise boron nitride nanotubestructures and/or independent boron nitride nanotubes, e.g.,compositions and aggregates that comprise boron nitride nanotubestructures and/or independent boron nitride nanotubes and in which thecombined amount of boron nitride nanotube structures and/or independentboron nitride nanotubes with dixie cup defects (defined below) and boronnitride nanotube structures and/or independent boron nitride nanotubeswith bamboo defects (defined below) is limited to being below (or notgreater than) specific percentages.

In accordance with a fifth aspect of the present inventive subjectmatter, there is provided a composition that comprises at least tenindependent boron nitride nanotubes (as defined herein) that have alength of at least 50 nm, in which:

-   -   among a sum of [1] the independent boron nitride nanotubes in        the composition that have a length of at least 50 nm, and [2]        boron nitride nanotube structures (as also defined herein) in        the composition that have a length of at least 50 nm, not more        than 1% of said sum have at least one defect selected from among        dixie cup defects (as also defined herein) and bamboo defects        (as also defined herein).

In accordance with a sixth aspect of the present inventive subjectmatter, there is provided an aggregate that comprises a one-piecestructure comprising a plurality of independent boron nitride nanotubes(as defined herein), the one-piece structure having a first dimension ofat least 100 nm and a second dimension of at least 100 nm, the seconddimension perpendicular to the first dimension, in which:

-   -   among a sum of [1] the independent boron nitride nanotubes in        the one-piece structure that have a length of at least 50 nm,        and [2] boron nitride nanotube structures (as also defined        herein) in the one-piece structure that have a length of at        least 50 nm, not more than 1% of said sum have at least one        defect selected from among dixie cup defects (as also defined        herein) and bamboo defects (as also defined herein).

The present inventive subject matter also relates to compositions andaggregates that comprise boron nitride nanotube structures and/orindependent boron nitride nanotubes in which the quantity of single-wallboron nitride nanotube structures and/or independent boron nitridenanotubes, in relation to the quantity of multi-wall boron nitridenanotube structures and/or independent boron nitride nanotubes, is above(or at least) specific percentages.

In accordance with a seventh aspect of the present inventive subjectmatter, there is provided a composition that comprises at least tenindependent boron nitride nanotubes (as defined herein), in which:

-   -   among a sum of [1] the independent boron nitride nanotubes in        the composition that have a length of at least 50 nm, and [2]        boron nitride nanotube structures (as also defined herein) in        the composition that have a length of at least 50 nm, each of at        least 50% of said sum is single-wall (as also defined herein).

In accordance with an eighth aspect of the present inventive subjectmatter, there is provided an aggregate that comprises a one-piecestructure comprising at least one independent boron nitride nanotube (asdefined herein), the one-piece structure having a first dimension of atleast 100 nm and a second dimension of at least 100 nm, the seconddimension perpendicular to the first dimension, in which:

-   -   among a sum of [1] the independent boron nitride nanotubes in        the one-piece structure that have a length of at least 50 nm,        and [2] boron nitride nanotube structures (as also defined        herein) in the one-piece structure that have a length of at        least 50 nm, each of at least 50% of said sum is single-wall (as        also defined herein).

The present inventive subject matter also provides novel methods ofmaking the novel and unforeseen materials, compositions and aggregates.

In accordance with a ninth aspect of the present inventive subjectmatter, there is provided a method of making a composition, comprising:

-   -   supplying to a first region of a chamber a mixture of nitrogen        gas and hydrogen gas;    -   converting at least a portion of the mixture of nitrogen gas and        hydrogen gas to plasma;    -   supplying to a second region of the chamber a mixture of at        least one boron-containing material and nitrogen gas, whereby        the mixture of at least one boron-containing material and        nitrogen gas contacts the plasma to form a reaction mixture;    -   converting at least a portion of the mixture to epitaxial        h-BN/BNNT structures.

The inventive subject matter may be more fully understood with referenceto the accompanying drawings and the following detailed description ofthe inventive subject matter.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

FIG. 1 schematically depicts a representative embodiment of an apparatus10 that can be used to make epitaxial h-BN/BNNT structures, as well ascompositions and/or aggregates that comprise epitaxial h-BN/BNNTstructures, in accordance with the first and second aspects of thepresent inventive subject matter.

FIG. 2 is an enlarged portion of FIG. 1 .

FIG. 3 is an illustration of an epitaxial h-BN/BNNT structure

FIG. 4 is a TEM image of a representative portion of the product ofExample 1, in which each of about 30% of the boron nitride nanotubestructures were at least 30% covered by epitaxial hexagonal boronnitride.

FIG. 5 is a TEM image of a representative portion of the product ofExample 2, in which each of about 90% of the boron nitride nanotubestructures were at least 30% covered by epitaxial hexagonal boronnitride.

FIG. 6 is a TEM image of a portion of the product of Example 2, theimage showing (inter alia) epitaxial h-BN/BNNT structures.

FIG. 7 is a TEM image of a portion of the product of Example 2, theimage showing (inter alia) independent hexagonal boron nitride andepitaxial h-BN/BNNT structures (one of which comprises a clump of boronnitride nanotube structures).

FIG. 8 is a TEM image of a portion of the product of Example 2, theimage showing (inter alia) a clump of boron nitride nanotube structuresand epitaxial h-BN/BNNT structures.

FIG. 9 is a TEM image of a portion of the product of Example 2, theimage showing (inter alia) epitaxial h-BN/BNNT structures.

FIG. 10 is a TEM image of a portion of the product of Example 2, theimage showing (inter alia) residual boron and epitaxial h-BN/BNNTstructures.

FIG. 11 is a TEM image of a portion of the product of Example 2, theimage showing (inter alia) residual boron and epitaxial h-BN/BNNTstructures.

FIG. 12 is a TEM image of a portion of the product of Example 2, theimage showing (inter alia) epitaxial h-BN/BNNT structures.

FIG. 13 is a TEM image of an independent boron nitride nanotube.

DETAILED DESCRIPTION OF THE INVENTIVE SUBJECT MATTER

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this inventive subject matterbelongs. It will be further understood that terms, such as those definedin commonly used dictionaries, should be interpreted as having a meaningthat is consistent with their meaning in the context of the relevant artand the present disclosure and will not be interpreted in an idealizedor overly formal sense unless expressly so defined herein.

Although the terms “first”, “second”, etc. are used herein in referringto various structures, epitaxial h-BN/BNNT structures, boron nitridenanotube structures, hexagonal boron nitride structures, members,percentages, ranges of percentages, dimensions, regions, and connectionsections, such structures, epitaxial h-BN/BNNT structures, boron nitridenanotube structures, hexagonal boron nitride structures, members,percentages, ranges of percentages, dimensions, regions, connectionsections are not limited by these numerical terms. These numerical termsare used only to identify individually each structure, epitaxialh-BN/BNNT structure, boron nitride nanotube structure, hexagonal boronnitride structure, member, percentage, range of percentages, dimension,region, or connection section, and/or to distinguish one structure,epitaxial h-BN/BNNT structure, boron nitride nanotube structure,hexagonal boron nitride structure, member, percentage, range ofpercentages, dimension, region, or connection section from another.

The expression “each” is used in many places in the presentspecification, in connection with a feature (or features) in pluralitiesof items (or in “at least one” item or the like) in order to indicatethat the feature (or features) is/are present in each of the specifieditems (or individual item), as opposed to a feature that is somehowprovided by a plurality of items and not necessarily by an individualitem, or as opposed to a feature that is an average of the feature withrespect to a plurality of items. Such uses of the expression “each” takea variety of forms, e.g.:

-   -   “materials that each comprise an arrangement of atoms . . . ,”    -   “multiple layers which are each generally tubular and coaxial,”    -   “one or more layers (i.e., walls), each layer consisting of a        generally tubular arrangement of boron atoms and nitrogen        atoms,”    -   “each of at least 50% of said sum is single-wall,”    -   “each of the at least one hexagonal boron nitride structure(s)        is/are epitaxial with respect to the boron nitride nanotube        structure,”    -   “each epitaxial h-BN/BNNT structure includes a boron nitride        nanotube structure and at least one hexagonal boron nitride        structure,”    -   “hexagonal boron nitride structures that are each epitaxial with        respect to the boron nitride nanotube structure,”    -   “a structure that comprises (or a plurality of structures that        each comprise),”    -   “for each of at least 10% of the atoms in the outermost wall of        the boron nitride nanotube structure, there is an atom that [1]        is in a hexagonal boron nitride structure that is epitaxial with        respect to the boron nitride nanotube structure, and that [2] is        within 10 nanometers of such atom,”    -   “each of a quantity of boron nitride nanotube structures that is        at least 10% of the sum of [1] the quantity of independent boron        nitride nanotubes in the composition that have a length of at        least 50 nm, and [2] the quantity of boron nitride nanotube        structures in the composition that have a length of at least 50        nm:        -   the boron nitride nanotube structure has a length of at            least 50 nm, and a total of at least 10% of the outermost            wall of the boron nitride nanotube structure is covered by            hexagonal boron nitride structures that are each epitaxial            with respect to the boron nitride nanotube structure,” and    -   “each of at least some of said sum . . . ”

As noted above, in accordance with a first aspect of the presentinventive subject matter, there is provided a composition comprising atleast a first epitaxial h-BN/BNNT structure, the first epitaxialh-BN/BNNT structure comprising at least a first boron nitride nanotubestructure and at least a first hexagonal boron nitride structure, thefirst hexagonal boron nitride structure epitaxial with respect to thefirst boron nitride nanotube structure.

The expression “epitaxial h-BN/BNNT structure,” as used herein, refersto a novel and unforeseen structure provided by the present inventivesubject matter, namely, a structure that comprises a boron nitridenanotube structure (defined below) and at least one hexagonal boronnitride structure (defined below), in which each of the at least onehexagonal boron nitride structure(s) is/are epitaxial with respect tothe boron nitride nanotube structure. Accordingly, each epitaxialh-BN/BNNT structure includes a boron nitride nanotube structure and atleast one hexagonal boron nitride structure.

As is well known by persons of skill in the art, the expression“epitaxial” is used extensively in relation to crystal nucleation andcrystal growth.

A crystal is defined as atoms, molecules or ions arranged in an orderlyrepeating pattern—a crystal lattice—extending in all three spatialdimensions. Crystal growth is the process where a pre-existing crystalbecomes larger as more atoms, molecules or ions are added in theirordered positions in the crystal lattice. During crystal growth, theatoms, molecules or ions must fall into the correct lattice positions inorder for a well-ordered crystal to grow. When atoms, molecules or ionsfall into positions different from those in the idealized crystallattice, defects are formed. Typically, the atoms, molecules or ions ina crystal lattice are held in place, i.e., they cannot readily move fromtheir positions, and so crystal growth is often irreversible in thatonce the molecules or ions have fallen into place in the growinglattice, they are fixed.

Crystallization is typically understood as consisting of two processes,namely, crystal nucleation and crystal growth. Crystal nucleation iswhere a new crystal is formed (i.e., there is no pre-existing crystal;crystal growth is where a atoms, molecules or ions are added to anexisting crystal, i.e., a crystal that has been nucleated (andoptionally grown, i.e., adding to a crystal that has been nucleated isreferred to as crystal growth; adding to a crystal that has beennucleated and already grown to some degree is also referred to a crystalgrowth).

Epitaxy refers to nucleating a crystal of a particular orientation onanother crystal, where the orientation is determined by the underlyingcrystal. A statement herein that a first structure (i.e., a hexagonalboron nitride structure) is epitaxial with respect to a second structure(i.e., a boron nitride nanotube structure), means that [1] the atoms inthe second structure, and [2] the atoms in the first structure that areclosest to the second structure, are arranged relative to each other inthe manner that atoms in an idealized structure corresponding to thesecond structure are arranged relative to each other, i.e., they arearranged in the manner that results from (or would result from)nucleating the second structure on the first structure and growing thesecond structure on the nucleated second structure.

Accordingly, the expression “hexagonal boron nitride structure that isepitaxial with respect to the boron nitride nanotube structure” (andanalogous expressions, e.g., “hexagonal boron nitride structures thatare each epitaxial with respect to the boron nitride nanotubestructure,” “each of the at least one hexagonal boron nitridestructure(s) is/are epitaxial with respect to the boron nitride nanotubestructure,” “hexagonal boron nitride that is epitaxial with respect tothe boron nitride nanotube structure,” etc.), as used herein, means thatfor each such hexagonal boron nitride structure, [1] the atoms in thehexagonal boron nitride structure, and [2] the atoms in the boronnitride nanotube structure that are closest to the hexagonal boronnitride structure, are arranged relative to each other in the mannerthat atoms in an idealized hexagonal boron nitride structure (discussedbelow) are arranged relative to each other, i.e., they are arranged inthe manner that results from (or would result from) nucleating ahexagonal boron nitride structure on a boron nitride nanotube structureand growing the hexagonal boron nitride structure on the nucleatedhexagonal boron nitride structure.

Hexagonal boron nitride is characterized by stacking of two-dimensionalhoneycomb lattices made of boron and nitrogen atoms that are stronglybound by highly polar B—N bonds. The layers of hexagonal boron nitridegenerally stack in an AA′ stacking mode, i.e., a boron atom bearing apartial positive charge in one layer resides on the oppositely chargednitrogen atoms on the adjacent layers.

The expression “boron nirtide nanotube structure” is used herein torefer to a portion of an epitaxial h-BN/BNNT structure in which boronatoms and nitrogen atoms are in an arrangement of atoms that has a tenpercent or lower defect ratio relative to an idealized boron nitridenanotube (discussed above) of the same length, diameter and number ofwalls.

The expression “defect ratio,” as used herein, refers to the percentageof atoms in a structure that are misplaced relative to an idealizedstructure, i.e., the expression “arrangement of atoms that has a tenpercent or lower defect ratio relative to an idealized boron nitridenanotube,” as used herein, encompasses structures in which theproportion of deviations from an idealized boron nitride nanotube (ofthe same length, diameter, and number of walls) is not more than 10percent, such deviations being quantified in terms of the number ofatoms in the actual boron nitride nanotube structure that are inpositions that do not correspond to their respective positions in theidealized boron nitride nanotube, divided by the total number ofpositions for atoms in the idealized boron nitride nanotube (or bysubtracting, from 100 percent, the percentage of atoms in the actualboron nitride nanotube structure that are in positions that correspondto their respective positions in the idealized boron nitride nanotubevs. the total number of positions in the idealized boron nitridenanotube). A single deviation is where a single atom in the idealizedboron nitride nanotube is replaced by a different atom, or where asingle shift occurs. For example, in comparing the arrangement of atomsin an actual boron nitride nanotube structure with the arrangement ofatoms in an idealized boron nitride nanotube, a single set of deviationscan encompass a sequence of atoms (one atom wide) extending around theactual boron nitride nanotube structure, with the atoms on therespective opposite sides of the sequence of atoms (and not includingthe sequence of atoms) being compared to the arrangement of atoms in theidealized boron nitride nanotube.

As noted above, a hypothetical idealized boron nitride nanotube consistsof one or more layers (i.e., walls), each layer consisting of agenerally tubular arrangement of boron atoms and nitrogen atoms, theboron atoms and nitrogen atoms arranged in a repeating hexagonal patternin which boron atoms and nitrogen atoms alternate.

The expression “hexagonal boron nitride structure,” as used herein,refers to a portion of an epitaxial h-BN/BNNT structure in which atomsof boron and nitrogen are in an arrangement of atoms that has a tenpercent or lower defect ratio relative to an idealized hexagonal boronnitride structure (discussed below) of the same shape and number oflayers.

As above, the expression “defect ratio,” as used herein, refers to thepercentage of atoms in a structure that are misplaced relative to anidealized structure. In this context, i.e., in the expression “tenpercent or lower defect ratio relative to an idealized hexagonal boronnitride structure (discussed below) of the same shape and number oflayers,” a defect ratio of ten percent or lower encompasses structuresin which the proportion of deviations from an idealized hexagonal boronnitride structure, of the same shape and number of layers, is not morethan 10 percent, such deviations being quantified in terms of the numberof atoms in the actual arrangement of atoms that are in positions thatdo not correspond to their respective positions in the idealizedhexagonal boron nitride structure, divided by the total number ofpositions for atoms in the idealized hexagonal boron nitride structure,and expressed as a percentage (or by subtracting, from 100 percent, thepercentage of atoms in the actual arrangement of atoms that are inpositions that correspond to their respective positions in the idealizedhexagonal boron nitride structure vs. the total number of positions inthe idealized hexagonal boron nitride structure). A single deviation iswhere a single atom in the idealized hexagonal boron nitride structureis replaced by a different atom, or where a single shift occurs. Forexample, in comparing the arrangement of atoms in an actual materialwith the arrangement of atoms in an idealized hexagonal boron nitridestructure, a single set of deviations encompasses a sequence of atoms(one atom wide) extending across the actual material, with the atoms onthe respective opposite sides of the sequence of atoms (and notincluding the sequence of atoms) being compared to the arrangement ofatoms in the idealized hexagonal boron nitride structure.

The expression “idealized hexagonal boron nitride structure,” as usedherein, refers to a hypothetical ideal boron nitride structure thatconsists of one or more layers, each layer consisting of an arrangementof boron atoms and nitrogen atoms that corresponds to defect-freehexagonal boron nitride crystal. As is well known to persons of skill inthe art, the boron atoms and nitrogen atoms in hexagonal boron nitridecrystal are arranged in a repeating hexagonal pattern in which boronatoms and nitrogen atoms alternate.

The expression “hexagonal boron nitride region,” as used herein, refersto a region (e.g., a region of a one-piece unitary structure) of ahexagonal boron nitride structure.

The expression “hexagonal boron nitride” is used herein to refer to oneor more hexagonal boron nitride structures.

The expression “boron and nitrogen atoms nucleated on a boron nitridenanotube structure,” as used herein, refers to, from among all of theboron and nitrogen atoms in hexagonal boron nitride structures that areeach epitaxial with respect to the boron nitride nanotube structure,only those boron and nitrogen atoms that abut atoms in the boron nitridenanotube structure, i.e., only those boron and nitrogen atoms that arearranged in the manner that results from (or would result from)nucleating hexagonal boron nitride on a boron nitride nanotubestructure. For example, if hexagonal boron nitride is nucleated andgrown on a boron nitride nanotube structure, the expression “boron andnitrogen atoms nucleated on a boron nitride nanotube structure” refersto only the boron and nitrogen atoms that are nucleated on the boronnitride nanotube structure, and not the boron and nitrogen atoms thatare subsequently grown on the nucleated boron and nitrogen atoms.

Thus, the expression “hexagonal boron nitride that is epitaxial withrespect to the boron nitride nanotube structure” (defined above) differsfrom the expression “boron and nitrogen atoms nucleated on a boronnitride nanotube structure” in that the expression “hexagonal boronnitride that is epitaxial with respect to the boron nitride nanotubestructure” refers to all of the atoms in all of the hexagonal boronnitride structures that are epitaxial with respect to the boron nitridenanotube structure (not just the boron and nitrogen atoms nucleated onthe boron nitride nanotube).

The expression “independent boron nitride nanotube” is used herein torefer to a structure that comprises boron atoms and nitrogen atoms in anarrangement of atoms [1] that has a ten percent or lower defect ratiorelative to an idealized boron nitride nanotube (as discussed above) ofthe same length, diameter and number of walls, and [2] with respect towhich there is no hexagonal boron nitride structure that is epitaxial(i.e., there is no hexagonal boron nitride that is epitaxial withrespect to the nitrogen and boron atoms in the arrangement of atoms thathas a ten percent or lower defect ratio relative to an idealized boronnitride nanotube).

The expression “independent hexagonal boron nitride” is used herein torefer to a structure that comprises (or a plurality of structures thateach comprise) boron atoms and nitrogen atoms in an arrangement of atoms[1] that has a ten percent or lower defect ratio relative to anidealized hexagonal boron nitride structure (as discussed above) of thesame shape and number of layers, and [2] with respect to which there isno boron nitride nanotube structure that is epitaxial (i.e., there is noboron nitride nanotube with respect to which the arrangement of atomsthat has a ten percent or lower defect ratio relative to an idealizedhexagonal boron nitride structure is epitaxial).

As discussed below, one of the characteristics of epitaxial h-BN/BNNTstructures disclosed herein is that hexagonal boron nitride structures(that are epitaxial with respect to boron nitride nanotube structures)is readily perceived (e.g., by normal human vision) to “cover” boronnitride nanotube structures (partially or completely). The presentspecification includes definitions by which, for any particular boronnitride nanotube structure, the extent to which the boron nitridenanotube structure is covered by hexagonal boron nitride structures canbe quantified as a percentage. In order for such quantifications to bedefinite (i.e., extremely precise), such that a person of skill in theart can readily determine whether any particular structure satisfies anexpression herein relating to such coverage, and/or to determine whetherany particular composition or aggregate satisfies an expression relatingto at least a specific percentage of boron nitride nanotube structureseach being covered at least a specific percentage, the presentspecification includes (below) very detailed definitions to make suchcalculations sufficiently precise.

The expression “a total of at least 10% of the outermost wall of theboron nitride nanotube structure is covered by hexagonal boron nitridestructures that are each epitaxial with respect to the boron nitridenanotube structure,” as used herein, means that for each of at least 10%of the atoms in the outermost wall of the boron nitride nanotubestructure, there is an atom that [1] is in a hexagonal boron nitridestructure that is epitaxial with respect to the boron nitride nanotubestructure, and that [2] is within 10 nanometers of such atom.

The expression “outermost wall,” as used herein in relation to a boronnitride nanotube structure, refers to the outermost wall of a multi-wallboron nitride nanotube structure (i.e., the wall that is farthest fromthe axis of the boron nitride nanotube structure, and farthest from thespace within the tube) or (in the case of a single-wall boron nitridenanotube structure), the single wall.

The expression “outermost wall,” as used herein in relation to anindependent boron nitride nanotube, refers to the outermost wall of anindependent multi-wall boron nitride nanotube (i.e., the wall that isfarthest from the axis of the independent boron nitride nanotube, andfarthest from the space within the tube) or (in the case of anindependent single-wall boron nitride nanotube), the single wall.

In addition to the above definitions relating to the calculation ofpercentages to which boron nitride nanotube structures are covered byhexagonal boron nitride structures in epitaxial h-BN/BNNT structures,there are also epitaxial h-BN/BNNT structures in which a plurality ofboron nitride nanotube structures might be clumped together, and theentire clump (which includes multiple boron nitride nanotube structures)might be covered (at least to a percentage) by hexagonal boron nitridestructures that are epitaxial to boron nitride nanotube structures(e.g., outermost ones) in the clump. In order for such quantificationsto be sufficiently precise that a person of skill in the art can readilydetermine whether any particular structure satisfies an expressionherein relating to such coverage, and/or to determine whether anyparticular composition or aggregate satisfies an expression relating tosuch coverage, the present specification includes additional definitions(starting with a definition of “clump” and specific types of clumps) tomake such calculations sufficiently precise.

The expression “clump,” as used herein (e.g., in the expressions“independent boron nitride nanotube clump,” “boron nitride nanotubestructure clump,” and “boron nitride nanotube structure/independentboron nitride nanotube clump”) means a group of at least two independentboron nitride nanotubes that are all in contact with one another, atleast two boron nitride nanotube structures that are all in contact withone another, or at least one independent boron nitride nanotube and atleast one boron nitride nanotube structure that are all in contact withone another. A single “clump” refers to such a group in which eachmember of the group is in direct contact or indirect contact with everyother member of the group (indirect contact between respective membersof the group meaning that while the members are not in direct contactwith each other, a series of direct-contact pairs of members thatextends between the member, i.e., first and second members are in directcontact with each other, a third member is in direct contact with atleast one of the first and second members, a fourth member is in directcontact with at least one of the first through third members, a fifthmember is in direct contact with at least one of the first throughfourth members, etc.). A representative example where a “clump” isimportant in the context of the present inventive subject matter isdiscussed after the definition of “exterior atoms . . . ,” below.

The expression “independent boron nitride nanotube clump,” as usedherein, refers to a clump that comprises plural independent boronnitride nanotubes and no boron nitride nanotube structures.

The expression “boron nitride nanotube structure clump,” as used herein,refers to a clump that comprises plural boron nitride nanotubestructures and no independent boron nitride nanotubes.

The expression “boron nitride nanotube structure/independent boronnitride nanotube clump,” as used herein, refers to a clump thatcomprises at least one boron nitride nanotube structure and at least oneindependent boron nitride nanotube. Analogous expressions refer toanalogous structures, e.g., analogously, a clump of any specified number(or range) of boron nitride nanotube structures and/or independent boronnitride nanotubes refers to a structure in which the sum of [1] thetotal number of boron nitride nanotube structures and [2] the totalnumber of independent boron nitride nanotubes equals such specifiednumber (or is within the specified range).

The expression “a total of at least 10% of the exterior atoms of [2] theboron nitride nanotube structure clump, [3] the boron nitride nanotubestructure/independent boron nitride nanotube clump, or [5] the boronnitride nanotube structure that is not in a clump,

-   -   is covered by hexagonal boron nitride structures that are each        epitaxial with respect to a boron nitride nanotube structure in        [2] the boron nitride nanotube structure clump, [3] the boron        nitride nanotube structure/independent boron nitride nanotube        clump, or [5] the boron nitride nanotube structure that is not        in a clump,”        as used herein, means that for each of at least 10% of the        exterior atoms (defined below) of [2] the boron nitride nanotube        structure clump, [3] the boron nitride nanotube        structure/independent boron nitride nanotube clump, or [5] the        boron nitride nanotube structure that is not in a clump, there        is an atom [a] that is in a hexagonal boron nitride structure        that is epitaxial with respect to a boron nitride nanotube in        the clump, and [b] that is within 10 nanometers of such exterior        atom.

The expression “exterior atoms of [2] the boron nitride nanotubestructure clump, [3] the boron nitride nanotube structure/independentboron nitride nanotube clump, or [5] the boron nitride nanotubestructure that is not in a clump,” as used herein, encompasses any atomon [2] the boron nitride nanotube structure clump, [3] the boron nitridenanotube structure/independent boron nitride nanotube clump, or [5] theboron nitride nanotube structure that is not in a clump, for which thereexists a cylindrical region having a radius of 0.1 angstroms abuttingthe atom and extending away from the atom for at least 1 mm withoutintersecting with any other atom on the [2] the boron nitride nanotubestructure clump, [3] the boron nitride nanotube structure/independentboron nitride nanotube clump, or [5] the boron nitride nanotubestructure that is not in a clump.

A representative example where a “clump” is important in the context ofthe present inventive subject matter is where one or more boron nitridenanotube structures and/or one or more independent boron nitridenanotubes in a clump are substantially completely covered by other boronnitride nanotube structures and/or independent boron nitride nanotubes(e.g., such substantially completely covered boron nitride nanotubestructures and/or one or more independent boron nitride nanotubes are inthe middle of a large clump). In such a situation, the atoms of suchsubstantially completely boron nitride nanotube structures and/or one ormore independent boron nitride nanotubes would, in accordance with thedescription herein, not satisfy the definition above of an “exterioratom,” and so such atoms would not be considered in determining whetherthe expression “a total of at least 10% of the exterior atoms of [2] theboron nitride nanotube structure clump, [3] the boron nitride nanotubestructure/independent boron nitride nanotube clump, or [5] the boronnitride nanotube structure that is not in a clump,

-   -   is covered by hexagonal boron nitride structures that are each        epitaxial with respect to a boron nitride nanotube structure in        [2] the boron nitride nanotube structure clump, [3] the boron        nitride nanotube structure/independent boron nitride nanotube        clump, or [5] the boron nitride nanotube structure that is not        in a clump”        is satisfied.

The expression “residual boron,” as used herein, refers to clumpsconsisting of (or mostly consisting of) boron and/or boron compounds.

The expression “aggregate”, as used herein, refers to a one-pieceunitary structure, i.e., an integral structure, i.e., a structure thatcould be lifted by grasping any portion of the structure and lifting(i.e., such portion could be grasped and lifted without gravity causingany portion of the structure to fall apart from any other portion of thestructure).

The expression “one-piece unitary structure”, as used herein, refers toa structure that is a single piece.

The expression “plurality,” as used herein, means two or more (e.g., theexpression “plurality of hexagonal boron nitride structures” means twoor more hexagonal boron nitride structures).

The expression “not more than” a specified quantity, as used herein,means the specified quantity or fewer (e.g., the expression “not morethan 35% of the mass of the composition” means 35% or less of the massof the composition.

The expression “at least” a specified quantity, as use herein, means thespecified quantity or more (e.g., the expression “at least ten boronnitride nanotube structures” means ten boron nitride nanotube structuresor more), and vice-versa (e.g., the expression “two or more boronnitride nanotube structures” means at least two boron nitride nanotubestructures).

The expression “[a composition or aggregate] comprises at least [aspecified percent] of [a type of material]” (e.g., “the compositioncomprises at least 10% by mass of hexagonal boron nitride”) means thatthe specified type of material accounts for the specified percentage (orrange of percentages) among the entire composition or aggregate, andvice-versa (i.e., the expression “[a specified material] accounts for [aspecified percent] of [a composition or aggregate] means that thespecified percentage (or range of percentages) of the composition oraggregate is the specified material.

In expressions in which “a sum” is characterized as a sum of therespective values for two or more items, e.g., in the expressions:

-   -   “a sum of [1] a total mass of any independent hexagonal boron        nitride in the composition and [2] a total mass of any residual        boron in the composition,”    -   “a sum of [1] the independent boron nitride nanotubes in the        composition that have a length of at least 50 nm, and [2] boron        nitride nanotube structures in the composition that have a        length of at least 50 nm,”    -   “a sum of respective quantities of [1] independent boron nitride        nanotube clumps in the composition that have a length of at        least 50 nm, [2] boron nitride nanotube structure clumps in the        composition that have a length of at least 50 nm, [3] boron        nitride nanotube structure/independent boron nitride nanotube        clumps in the composition that have a length of at least 50 nm,        [4] independent boron nitride nanotubes in the composition that        are not in a clump and that have a length of at least 50 nm, and        [5] boron nitride nanotube structures in the composition that        are not in a clump and that have a length of at least 50 nm,”        and similar expressions in which “composition” is replaced by        and/or included with “one-piece structure,” it is possible that        one or more of the values is zero, i.e., the inclusion of an        item does not mean that the value for such item is necessarily        non-zero.

The expressions “plasma” and “ionized gas” are used herein in accordancewith their well known meaning to refer to matter that results whensufficient energy is provided to a gas to free electrons from atoms ormolecules and to thus allow ions and electrons to coexist (also referredto as the fourth state of matter, i.e., solid, liquid, gas, plasma).

As noted above, in accordance with a first aspect of the presentinventive subject matter, there is provided a composition comprising:

-   -   at least a first epitaxial h-BN/BNNT structure,    -   the first epitaxial h-BN/BNNT structure comprising at least a        first boron nitride nanotube structure and at least a first        hexagonal boron nitride structure,    -   the first hexagonal boron nitride structure epitaxial with        respect to the first boron nitride nanotube structure.

In some embodiments according to the first aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein:

-   -   a sum of [1] a quantity of independent boron nitride nanotubes        in the composition that have a length of at least 50 nm, and [2]        a quantity of boron nitride nanotube structures in the        composition that have a length of at least 50 nm, is at least        ten, and    -   for each of a quantity of boron nitride nanotube structures that        is at least 10% of the sum of [1] the quantity of independent        boron nitride nanotubes in the composition that have a length of        at least 50 nm, and [2] the quantity of boron nitride nanotube        structures in the composition that have a length of at least 50        nm:        -   the boron nitride nanotube structure has a length of at            least 50 nm, and a total of at least 10% of the outermost            wall of the boron nitride nanotube structure is covered by            hexagonal boron nitride structures that are each epitaxial            with respect to the boron nitride nanotube structure,            and in some of such embodiments:    -   for each of a quantity of boron nitride nanotube structures that        is at least a first percentage (selected from among 20%, 30%,        40%, 50%, 60%, 70%, 80%, and 90%), or that is within a first        range of percentages (selected from among 10%-20%, 20%-30%,        30%-40%, 40%-50%, 50%-60%, 60%-70%, 70%-80%, and 80%-90%) of the        sum of [1] the quantity of independent boron nitride nanotubes        in the composition that have a length of at least 50 nm, and [2]        the quantity of boron nitride nanotube structures in the        composition that have a length of at least 50 nm:        -   the boron nitride nanotube structure has a length of at            least 50 nm, and a total of at least a second percentage            (selected from among 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%,            and 90%), or a total that is within a second range of            percentages (selected from among 10%-20%, 20%-30%, 30%-40%,            40%-50%, 50%-60%, 60%-70%, 70%-80%, and 80%-90%) of the            outermost wall of the boron nitride nanotube structure is            covered by hexagonal boron nitride structures that are each            epitaxial with respect to the boron nitride nanotube            structure,            including any combination of the first percentages (or first            range of percentages) and the second percentages (or second            range of percentages).

In some embodiments according to the first aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein:

-   -   a sum of respective quantities of [1] independent boron nitride        nanotube clumps in the composition that have a length of at        least 50 nm, [2] boron nitride nanotube structure clumps in the        composition that have a length of at least 50 nm, [3] boron        nitride nanotube structure/independent boron nitride nanotube        clumps in the composition that have a length of at least 50 nm,        [4] independent boron nitride nanotubes in the composition that        are not in a clump and that have a length of at least 50 nm, and        [5] boron nitride nanotube structures in the composition that        are not in a clump and that have a length of at least 50 nm, is        at least ten,    -   for each of a quantity that is at least 30% of said sum, among        [2] the boron nitride nanotube structure clumps in the        composition that have a length of at least 50 nm, [3] the boron        nitride nanotube structure/independent boron nitride nanotube        clumps in the composition that have a length of at least 50 nm,        and [5] the boron nitride nanotube structures in the composition        that are not in a clump and that have a length of at least 50        nm:    -   a total of at least 10% of exterior atoms of [2] the boron        nitride nanotube structure clump, [3] the boron nitride nanotube        structure/independent boron nitride nanotube clump, or [5] the        boron nitride nanotube structure that is not in a clump,    -   is covered by hexagonal boron nitride structures that are each        epitaxial with respect to a boron nitride nanotube structure in        [2] the boron nitride nanotube structure clump, [3] the boron        nitride nanotube structure/independent boron nitride nanotube        clump, or [5] the boron nitride nanotube structure that is not        in a clump,        and in some of such embodiments:    -   a sum of respective quantities of [1] independent boron nitride        nanotube clumps in the composition that have a length of at        least 50 nm, [2] boron nitride nanotube structure clumps in the        composition that have a length of at least 50 nm, [3] boron        nitride nanotube structure/independent boron nitride nanotube        clumps in the composition that have a length of at least 50 nm,        [4] independent boron nitride nanotubes in the composition that        are not in a clump and that have a length of at least 50 nm, and        [5] boron nitride nanotube structures in the composition that        are not in a clump and that have a length of at least 50 nm, is        at least ten,    -   for each of a quantity that is at least a first percentage        (selected from among 40%, 50%, 60%, 70%, 80%, and 90%), or that        is within a first range of percentages (selected from among        30%-40%, 40%-50%, 50%-60%, 60%-70%, 70%-80%, and 80%-90%) of        said sum, among [2] the boron nitride nanotube structure clumps        in the composition that have a length of at least 50 nm, [3] the        boron nitride nanotube structure/independent boron nitride        nanotube clumps in the composition that have a length of at        least 50 nm, and [5] the boron nitride nanotube structures in        the composition that are not in a clump and that have a length        of at least 50 nm:    -   a total of at least a second percentage (selected from among        10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%), or a total        that is within a second range of percentages (selected from        among 10%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-60%, 60%-70%,        70%-80%, and 80%-90%) of exterior atoms of [2] the boron nitride        nanotube structure clump, [3] the boron nitride nanotube        structure/independent boron nitride nanotube clump, or [5] the        boron nitride nanotube structure that is not in a clump,    -   is covered by hexagonal boron nitride structures that are each        epitaxial with respect to a boron nitride nanotube structure in        [2] the boron nitride nanotube structure clump, [3] the boron        nitride nanotube structure/independent boron nitride nanotube        clump, or [5] the boron nitride nanotube structure that is not        in a clump,        including any combination of the first percentages (or first        range of percentages) and the second percentages (or second        range of percentages).

As noted above, in accordance with a second aspect of the presentinventive subject matter, there is provided an aggregate comprising:

-   -   a one-piece structure comprising at least a first epitaxial        h-BN/BNNT structure,    -   the first epitaxial h-BN/BNNT structure comprising at least a        first boron nitride nanotube structure and at least a first        hexagonal boron nitride structure,    -   the first hexagonal boron nitride structure epitaxial with        respect to the boron nitride nanotube structure,    -   the one-piece structure having a first dimension of at least 100        nm and a second dimension of at least 100 nm, the second        dimension perpendicular to the first dimension.

In some embodiments according to the second aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein:

-   -   for each of a quantity of boron nitride nanotube structures in        the one-piece structure that is at least 10% of the sum of [1]        the quantity of independent boron nitride nanotubes in the        one-piece structure that have a length of at least 50 nm, and        [2] the quantity of boron nitride nanotube structures in the        one-piece structure that have a length of at least 50 nm:        -   a total of at least 10% of the outermost wall of the boron            nitride nanotube structure is covered by hexagonal boron            nitride structures that are each epitaxial with respect to            the boron nitride nanotube structure,            and in some of such embodiments:    -   for each of a quantity of boron nitride nanotube structures in        the one-piece structure that is at least a first percentage        (selected from among 20%, 30%, 40%, 50%, 60%, 70%, 80%, and        90%), or that is within a first range of percentages (selected        from among 10%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-60%, 60%-70%,        70%-80%, and 80%-90%) of the sum of [1] the quantity of        independent boron nitride nanotubes in the one-piece structure        that have a length of at least 50 nm, and [2] the quantity of        boron nitride nanotube structures in the one-piece structure        that have a length of at least 50 nm:        -   a total of at least a second percentage (selected from among            20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%), or a total that            is within a second range of percentages (selected from among            10%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-60%, 60%-70%,            70%-80%, and 80%-90%) of the outermost wall of the boron            nitride nanotube structure is covered by hexagonal boron            nitride structures that are each epitaxial with respect to            the boron nitride nanotube structure,            including any combination of the first percentages (or first            range of percentages) and the second percentages (or second            range of percentages).

In some embodiments according to the second aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein:

-   -   for each of a quantity among [2] boron nitride nanotube        structure clumps in the one-piece structure that have a length        of at least 50 nm, [3] boron nitride nanotube        structure/independent boron nitride nanotube clumps in the        one-piece structure that have a length of at least 50 nm, and        [5] boron nitride nanotube structures in the one-piece structure        that are not in a clump and that have a length of at least 50        nm,    -   that is at least 10% of a sum of respective quantities of [1]        independent boron nitride nanotube clumps in the one-piece        structure that have a length of at least 50 nm, [2] boron        nitride nanotube structure clumps in the one-piece structure        that have a length of at least 50 nm, [3] boron nitride nanotube        structure/independent boron nitride nanotube clumps in the        one-piece structure that have a length of at least 50 nm, [4]        independent boron nitride nanotubes in the one-piece structure        that are not in a clump and that have a length of at least 50        nm, and [5] boron nitride nanotube structures in the one-piece        structure that are not in a clump and that have a length of at        least 50 nm:        -   a total of at least 10% of exterior atoms of [2] the boron            nitride nanotube structure clump, [3] the boron nitride            nanotube structure/independent boron nitride nanotube clump,            or [5] the boron nitride nanotube structure that is not in a            clump,            -   is covered by hexagonal boron nitride structures that                are each epitaxial with respect to a boron nitride                nanotube structure in [2] the boron nitride nanotube                structure clump, [3] the boron nitride nanotube                structure/independent boron nitride nanotube clump, or                [5] the boron nitride nanotube structure that is not in                a clump,                and in some of such embodiments:    -   for each of a quantity among [2] boron nitride nanotube        structure clumps in the one-piece structure that have a length        of at least 50 nm, [3] boron nitride nanotube        structure/independent boron nitride nanotube clumps in the        one-piece structure that have a length of at least 50 nm, and        [5] boron nitride nanotube structures in the one-piece structure        that are not in a clump and that have a length of at least 50        nm,    -   that is at least a first percentage (selected from among 20%,        30%, 40%, 50%, 60%, 70%, 80%, and 90%), or that is within a        first range of percentages (selected from among 10%-20%,        20%-30%, 30%-40%, 40%-50%, 50%-60%, 60%-70%, 70%-80%, and        80%-90%) of a sum of respective quantities of [1] independent        boron nitride nanotube clumps in the one-piece structure that        have a length of at least 50 nm, [2] boron nitride nanotube        structure clumps in the one-piece structure that have a length        of at least 50 nm, [3] boron nitride nanotube        structure/independent boron nitride nanotube clumps in the        one-piece structure that have a length of at least 50 nm, [4]        independent boron nitride nanotubes in the one-piece structure        that are not in a clump and that have a length of at least 50        nm, and [5] boron nitride nanotube structures in the one-piece        structure that are not in a clump and that have a length of at        least 50 nm:        -   a total of at least a second percentage (selected from among            20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%), or a total that            is within a second range of percentages (selected from among            10%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-60%, 60%-70%,            70%-80%, and 80%-90%) of exterior atoms of [2] the boron            nitride nanotube structure clump, [3] the boron nitride            nanotube structure/independent boron nitride nanotube clump,            or [5] the boron nitride nanotube structure that is not in a            clump,            -   is covered by hexagonal boron nitride structures that                are each epitaxial with respect to a boron nitride                nanotube structure in [2] the boron nitride nanotube                structure clump, [3] the boron nitride nanotube                structure/independent boron nitride nanotube clump, or                [5] the boron nitride nanotube structure that is not in                a clump,                including any combination of the first percentages (or                first range of percentages) and the second percentages                (or second range of percentages).

As noted above, in accordance with a third aspect of the presentinventive subject matter, there is provided a composition, comprising:

-   -   a plurality of independent boron nitride nanotubes,    -   a sum of [1] a total mass of any independent hexagonal boron        nitride in the composition and [2] a total mass of any residual        boron in the composition accounts for not more than 35% of the        mass of the composition.

In some embodiments according to the third aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein:

-   -   a sum of [1] a total mass of any independent hexagonal boron        nitride in the composition and [2] a total mass of any residual        boron in the composition accounts for not more than a first        percentage (selected from among 30%, 25%, 20%, 15%, 10%, and        5%), or accounts for a percentage that is within a first range        of percentages (selected from among 30%-35%, 25%-30%, 20%-25%,        15%-20%, 10%-15%, and 5%-10%) of the mass of the composition.

As noted above, in accordance with a fourth aspect of the presentinventive subject matter, there is provided an aggregate, comprising:

-   -   a one-piece structure comprising a plurality of independent        boron nitride nanotubes,    -   the one-piece structure having a first dimension of at least 100        nm and a second dimension of at least 100 nm, the second        dimension perpendicular to the first dimension,    -   a sum of [1] a total mass of independent hexagonal boron nitride        in the one-piece structure and [2] a total mass of any residual        boron in the one-piece structure accounts for not more than 35%        of the mass of the one-piece structure.

In some embodiments according to the fourth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein:

-   -   a sum of [1] a total mass of any independent hexagonal boron        nitride in the one-piece structure and [2] a total mass of any        residual boron in the one-piece structure accounts for not more        than a first percentage (selected from among 30%, 25%, 20%, 15%,        10%, and 5%), or accounts for a percentage that is within a        first range of percentages (selected from among 30%-35%,        25%-30%, 20%-25%, 15%-20%, 10%-15%, and 5%-10%) of the mass of        the one-piece structure.

As noted above, in accordance with a fifth aspect of the presentinventive subject matter, there is provided a composition, comprising:

-   -   at least ten independent boron nitride nanotubes that have a        length of at least 50 nm,    -   among a sum of [1] the independent boron nitride nanotubes in        the composition that have a length of at least 50 nm, and [2]        boron nitride nanotube structures in the composition that have a        length of at least 50 nm, not more than 1% of said sum have at        least one defect selected from among dixie cup defects and        bamboo defects.

Persons of skill in the art are familiar with dixie cup defects andbamboo defects. For definiteness, the expression “bamboo defect,” asused herein with regard to a boron nitride nanotube, means that theboron nitride nanotube has plural regions in which a diameter of theboron nitride nanotube increases by at least 10% over a length of 5 nmor less (i.e., respective diameters of the boron nitride nanotube (i.e.,diameters perpendicular to the axis of the boron nitride nanotube) thatare spaced not more than 5 nm apart along the length of the boronnitride nanotube, differ by at least 10% (i.e., one diameter is at least1.1 times the other diameter)).

For definiteness, the expression “dixie cup defect,” as used herein withregard to a boron nitride nanotube (or a plurality of boron nitridenanotubes), means that the boron nitride nanotube (or each of the boronnitride nanotubes) is tapered, in that it has a first (wide) end and asecond (narrow) end (spaced along the axis of the boron nitride nanotubeor wall), with the second (narrow) end having a diameter (perpendicularto the axis) that is not more than 65% of the diameter of the first(wide) end, and in which the narrow end of the boron nitride nanotube isinside the wide end of another tapered boron nitride nanotube (i.e., aplane perpendicular to the axes of the boron nitride nanotubes and at aregion of “dixie cup overlap” would pass through both boron nitridenanotubes.

In some embodiments according to the fifth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein:

-   -   among a sum of [1] the independent boron nitride nanotubes in        the composition that have a length of at least 50 nm, and [2]        boron nitride nanotube structures in the composition that have a        length of at least 50 nm, not more than a first percentage        (selected from among 0.8%, 0.6%, 0.4%, 0.3%, 0.2% and 0.1%), or        a percentage that is within a first range of percentages        (selected from among 0.0%-0.1%, 0.1%-0.2%, 0.2%-0.3%, 0.3%-0.4%,        0.4%-0.6%, 0.6%-0.8%, and 0.8%-1.0%) of said sum have at least        one defect selected from among dixie cup defects and bamboo        defects.

As noted above, in accordance with a sixth aspect of the presentinventive subject matter, there is provided an aggregate, comprising:

-   -   a one-piece structure comprising a plurality of independent        boron nitride nanotubes,    -   the one-piece structure having a first dimension of at least 100        nm and a second dimension of at least 100 nm, the second        dimension perpendicular to the first dimension,    -   among a sum of [1] the independent boron nitride nanotubes in        the one-piece structure that have a length of at least 50 nm,        and [2] boron nitride nanotube structures in the one-piece        structure that have a length of at least 50 nm, not more than 1%        of said sum have at least one defect selected from among dixie        cup defects and bamboo defects.

In some embodiments according to the sixth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein:

-   -   among a sum of [1] the independent boron nitride nanotubes in        the one-piece structure that have a length of at least 50 nm,        and [2] boron nitride nanotube structures in the one-piece        structure that have a length of at least 50 nm, not more than a        first percentage (selected from among 0.8%, 0.6%, 0.4%, 0.3%,        0.2% and 0.1%), or a percentage that is within a first range of        percentages (selected from among 0.0%-0.1%, 0.1%-0.2%,        0.2%-0.3%, 0.3%-0.4%, 0.4%-0.6%, 0.6%-0.8%, and 0.8%-1.0%) of        said sum have at least one defect selected from among dixie cup        defects and bamboo defects.

As noted above, in accordance with a seventh aspect of the presentinventive subject matter, there is provided a composition, comprising:

-   -   at least ten independent boron nitride nanotubes,    -   among a sum of [1] the independent boron nitride nanotubes in        the composition that have a length of at least 50 nm, and [2]        boron nitride nanotube structures in the composition that have a        length of at least 50 nm, each of at least 50% of said sum is        single-wall.

In some embodiments according to the seventh aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, each of at least some ofsaid sum of [1] the independent boron nitride nanotubes in thecomposition that have a length of at least 50 nm, and [2] the boronnitride nanotube structures in the composition that have a length of atleast 50 nm, that is single-wall is in an independent boron nitridenanotube clump, a boron nitride nanotube structure clump, or a boronnitride nanotube structure/independent boron nitride nanotube clump.

In some embodiments according to the seventh aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, among a sum of [1] theindependent boron nitride nanotubes in the composition that have alength of at least 50 nm, and [2] boron nitride nanotube structures inthe composition that have a length of at least 50 nm, each of 50-60percent of said sum is single-wall.

As noted above, in accordance with an eighth aspect of the presentinventive subject matter, there is provided an aggregate, comprising:

-   -   a one-piece structure comprising at least one independent boron        nitride nanotube,    -   the one-piece structure having a first dimension of at least 100        nm and a second dimension of at least 100 nm, the second        dimension perpendicular to the first dimension,    -   among a sum of [1] the independent boron nitride nanotubes in        the one-piece structure that have a length of at least 50 nm,        and [2] boron nitride nanotube structures in the one-piece        structure that have a length of at least 50 nm, each of at least        50% of said sum is single-wall.

In some embodiments according to the eighth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, each of at least some ofsaid sum of [1] the independent boron nitride nanotubes in the one-piecestructure that have a length of at least 50 nm, and [2] the boronnitride nanotube structures in the one-piece structure that have alength of at least 50 nm, that is single-wall is in an independent boronnitride nanotube clump, a boron nitride nanotube structure clump, or aboron nitride nanotube structure/independent boron nitride nanotubeclump.

In some embodiments according to the eighth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, among a sum of [1] theindependent boron nitride nanotubes in the one-piece structure that havea length of at least 50 nm, and [2] boron nitride nanotube structures inthe one-piece structure that have a length of at least 50 nm, each of50-60 percent of said sum is single-wall.

In some embodiments according to any of the first, second, fifth, sixth,seventh and eighth aspects of the present inventive subject matter,which can include or not include, as suitable, any of the other featuresdescribed herein, the combined mass of the epitaxial h-BN/BNNTstructures in the composition accounts for at least 65% of the mass ofthe composition or one-piece structure (i.e., the composition withrespect to the first, third, fifth and seventh aspects, and theone-piece structure with respect to the second, fourth, sixth and eighthaspects, and similarly below in other occurrences of “composition orone-piece structure”),

and in some of such embodiments, the combined mass of the epitaxialh-BN/BNNT structures in the composition accounts for at least a firstpercentage (selected from among 70%, 75%, 80%, 85%, 90%, 95%, 97%, and99%), or accounts for a percentage that is within a first range ofpercentages (selected from among 65%-70%, 70%-75%, 75%-80%, 80%-85%,85%-90%, 90%-95%, 95%-97%, and 97%-99%) of the mass of the compositionor one-piece structure.

In some embodiments according to any of the first, second, third,fourth, fifth, sixth, seventh and eighth aspects of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, at least 10% by mass of thecomposition or one-piece structure comprises hexagonal boron nitridestructures that are each epitaxial with respect to a boron nitridenanotube structure.

In some embodiments according to any of the first, second, third,fourth, fifth, sixth, seventh and eighth aspects of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein for each of at least 10% ofthe atoms in the composition or one-piece structure, the atom is in ahexagonal boron nitride structure that is epitaxial with a boron nitridenanotube structure in the composition.

In some embodiments according to either of the first and second aspectsof the present inventive subject matter, which can include or notinclude, as suitable, any of the other features described herein, thecombined mass of any independent hexagonal boron nitride in thecomposition or one-piece structure and [2] the combined mass of anyamorphous boron in the composition or one-piece structure accounts forless than 35% of the mass of the composition or one-piece structure, and

in some of such embodiments, the combined mass of any independenthexagonal boron nitride in the composition or one-piece structure and[2] the combined mass of any amorphous boron in the composition orone-piece structure accounts for less than a first percentage (selectedfrom among 30%, 25%, 20%, 15%, 10% and 5%), or accounts for a percentagethat is within a first range of percentages (selected from among10%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-60%, 60%-70%, 70%-80%, and80%-90%) 35% of the mass of the composition or one-piece structure.

In some embodiments according to any of the first, second, third andfourth aspects of the present inventive subject matter, which caninclude or not include, as suitable, any of the other features describedherein, a sum of [1] the independent boron nitride nanotubes in thecomposition or one-piece structure that have a length of at least 50 nm,and [2] boron nitride nanotube structures in the composition orone-piece structure that have a length of at least 50 nm, not more than1% of said sum have at least one defect selected from among dixie cupdefects and bamboo defects, and

In some of such embodiments, a sum of [1] the independent boron nitridenanotubes in the composition or one-piece structure that have a lengthof at least 50 nm, and [2] boron nitride nanotube structures in thecomposition or one-piece structure that have a length of at least 50 nm,not more than a first percentage (selected from among 0.8%, 0.6%, 0.4%,0.3%, 0.2% and 0.1%), or a percentage that is within a first range ofpercentages (selected from among 0.0%-0.1%, 0.1%-0.2%, 0.2%-0.3%,0.3%-0.4%, 0.4%-0.6%, 0.6%-0.8%, and 0.8%-1.0%) of said sum have atleast one defect selected from among dixie cup defects and bamboodefects.

In some embodiments according to any of the first, second, third,fourth, fifth and sixth aspects of the present inventive subject matter,which can include or not include, as suitable, any of the other featuresdescribed herein, a sum of [1] the independent boron nitride nanotubesin the composition or one-piece structure that have a length of at least50 nm, and [2] boron nitride nanotube structures in the composition orone-piece structure that have a length of at least 50 nm, each of atleast 50% of said sum is single-wall.

In some embodiments according to either of the third and fourth aspectsof the present inventive subject matter, which can include or notinclude, as suitable, any of the other features described herein,independent hexagonal boron nitride accounts for not more than 1 percentby mass of the composition or aggregate, and

in some of such embodiments, independent hexagonal boron nitrideaccounts for not more than first percentage (selected from among 0.8%,0.6%, 0.4%, 0.3%, 0.2% and 0.1%), or accounts for a percentage that iswithin a first range of percentages (selected from among 0.0%-0.1%,0.1%-0.2%, 0.2%-0.3%, 0.3%-0.4%, 0.4%-0.6%, 0.6%-0.8%, and 0.8%-1.0%) bymass of the composition or aggregate

FIG. 1 schematically depicts a representative embodiment of an apparatus10 that can be used to make epitaxial h-BN/BNNT structures, as well ascompositions and/or aggregates that comprise epitaxial h-BN/BNNTstructures, in accordance with the first and second aspects of thepresent inventive subject matter. FIG. 2 is an enlarged portion of FIG.1 , showing portions of the apparatus 10.

The apparatus 10 comprises a plasma generator 11, a collar region 12, afirst reactor section 13 (which defines a first reaction chamber region)and a second reactor section 14 (which defines a second reaction chamberregion).

The plasma generator 11 comprises a wall 15, an electromagnetic wavegenerator and waveguide 16 and a sparker 17. The waveguide is aninductor, and is in the form of coil with several turns (normally fromthree to six), e.g., of copper tubing (¼″ and up). A copper coil is anon-magnetic coil that provides high electrical conductivity. A numberof turns is defined to match the inductor's inductance and electricalresistance, which provides matching with the high-frequency power supplyoutput.

The wall 15 of the plasma generator 11 comprises an RF-transparentregion 18 that is radio frequency-transparent (i.e., RF-transparent),electrically conductive and non-magnetic. A representative example of asuitable material out of which the RF-transparent region 18 can be madeis alumina.

An AC power supply 19 supplies radio frequency energy to theelectromagnetic wave generator 16, which generates electromagnetic wavesat a plurality of frequencies selected from within a range of tens ofkilohertz to thousands of gigahertz, and such electromagnetic waves passthrough the RF-transparent portion 18 of the wall 15 of the plasmageneration region 11.

A plasma generator space 21 is inside the plasma generator 11.

The sparker 17 comprises a movable electrode 29 and a dischargeprotrusion 30. The movable electrode 29 is configured to controllablyextend into a region of the plasma generator space 21 that comprisesmaximal magnetic field density and maximum electric field density. Thedischarge protrusion 30 is made of electrically conductive, non-magneticmaterial and is configured to create a discharge point when approachedby the movable electrode 29, such discharge creating a plasma. Themovable electrode 29 is configured to retract out of the region ofmaximal magnetic field density and maximum electric field density aftersuch discharge.

The plasma generator 11 has one or more ports 20 through which materials(e.g., nitrogen gas) can be introduced into the plasma generator space21.

The plasma generator 11 has a plume opening 22 through which a plume ofplasma generated in the plasma generator 11 enters a collar space 23inside the collar region 12.

The collar region 12 comprises at least one reactant feed opening 24through which feedstock (e.g., boron powder, boron nitride, boroncarbide, boron trioxide, boric acid, etc.), optionally along with acarrier gas, can be introduced (e.g., injected) into the collar space 23(and into the plasma plume).

The first reactor section 13 can comprise one or more access ports 25 toprovide access to the first reaction chamber region 26 inside the firstreactor section 13. The one or more access ports 25 (if included) canprovide access for diagnostics (such as optical monitoring of thereaction), for inserting structures into the reaction chamber (e.g.,quench modifiers, such as wires or meshes), or for removing product.

Similarly, the second reactor section 14 can comprise one or more accessports 27 to provide access to the second reaction chamber region 28inside the second reactor section 14. The one or more access ports 27(if included) can provide access for diagnostics (such as opticalmonitoring of the reaction), for inserting structures into the reactionchamber (e.g., quench modifiers, such as wires or meshes), or forremoving product.

The apparatus 10 further comprises an outer shell 31 outside the plasmagenerator 11 to enable cooling and/or to provide gas/liquid sealing. Inthe embodiment depicted in FIG. 1 , the outer shell 31 is substantiallycoaxial with respect to the plasma generator 11, with the plasmagenerator 11 as an inner tube and the outer shell 31 as an outer tube.Holes 32 at the ends of the outer shell 31 enable coolant, e.g. water,to flow into the bottom (in the orientation depicted) of a chamber 33within the outer shell 31 and out the top of the chamber 33. The outershell 31 also assists in sealing the plasma generator 11, therebyassisting in avoiding or reducing any plasma and gas leakage. The outershell 31 is preferably RF-transparent. Representative examples ofsuitable materials out of which the outer shell 31 can be made includequartz and ceramic materials.

In some embodiments, product can be removed from the first reactionchamber region 26 and/or the second reaction chamber region 28continuously or semi-continuously (e.g., by a conveyor that carriesproduct out of the first reaction chamber region 26 and/or the secondreaction chamber region 28) (i.e., rather than batch) operation.

An exit port 34 is formed in the second reactor section 14, and a firstexhaust line 35 is connected to the exit port 34. A pressure regulator36 is connected to the first exhaust line 35, and a second exhaust line37 is connected to the pressure regulator 36, whereby gases (e.g.,nitrogen, argon and hydrogen) can be exhausted and the pressure withinthe first and second reaction chamber regions 26 and 28 can beregulated. Any suitable pressure regulator (e.g., a needle valve) can beemployed as the pressure regulator 36.

In the discussion above, the plasma generator is an inductively coupledplasma generator. As an alternative, the plasma generator may instead bea DC arc plasma generator (i.e., a plasma generator driven by a DC powersource). Persons of skill in the art are familiar with DC arc plasmagenerators, and any such plasma generator arrangement can be use. Insome embodiments, an inductively coupled plasma generator isadvantageous (relative to a DC arc plasma generator) in the fabricationof compositions and/or aggregates that comprise boron nitride nanotubeswith hexagonal boron nitride structures that are epitaxial with respectto a boron nitride nanotube, because an inductively coupled plasmagenerator provides larger plasma volume, lower plasma gas velocity, andlonger reaction time. In addition, due to the absence of electrodes inan inductively coupled plasma generator, an inductively coupled plasmagenerator may be relatively maintenance free and (unlike a DC arc plasmagenerator, which must include electrodes) does not introducecontamination from electrodes in the materials being fabricated.

The power density and volume of the plasma plume are adjustable byvarying the input power to the plasma generator, by varying the pressurewithin the plasma generator space 21, and/or by varying the flow ratesof materials supplied to the apparatus 10 (e.g., nitrogen gas, boronpowder with nitrogen gas carrier, etc.).

The apparatus 10 depicted in FIG. 1 can also be used to make:

-   -   compositions (or aggregates) that comprise a plurality of        independent boron nitride nanotubes, in which a sum of [1] a        total mass of any independent hexagonal boron nitride in the        composition (or aggregate) and [2] a total mass of any residual        boron in the composition (or aggregate) accounts for not more        than 35% of the mass of the composition (or aggregate), in        accordance with the third aspect (or the fourth aspect) of the        present inventive subject matter;    -   compositions (or aggregates) that comprise at least ten        independent boron nitride nanotubes that have a length of at        least 50 nm, in which among a sum of [1] the independent boron        nitride nanotubes in the composition (or aggregate) that have a        length of at least 50 nm, and [2] boron nitride nanotube        structures in the composition (or aggregate) that have a length        of at least 50 nm, not more than 1% of said sum have at least        one defect selected from among dixie cup defects and bamboo        defects, in accordance with the fifth aspect (or the sixth        aspect) of the present inventive subject matter; and    -   compositions (or aggregates) that comprise at least ten        independent boron nitride nanotubes, in which among a sum of [1]        the independent boron nitride nanotubes in the composition (or        aggregate) that have a length of at least 50 nm, and [2] boron        nitride nanotube structures in the composition (or aggregate)        that have a length of at least 50 nm, each of at least 50% of        said sum is single-wall, in accordance with the seventh aspect        (or the eighth aspect) of the present inventive subject matter.

One specific representative embodiment of a method by which epitaxialh-BN/BNNT structure in accordance with the first aspect of the presentinventive subject matter can be made comprises:

-   -   supplying 50 liters per minute of a mixture of nitrogen and        hydrogen (96 parts by mass nitrogen and 4 parts by mass        hydrogen) into a plasma generator space 21 of an apparatus 10 as        depicted in FIG. 1 (through a port 20 of an apparatus 10 as        depicted in FIG. 1 ), the apparatus further characterized in        that the outside diameter of the plasma generator 11 is 3.5        inches, the inside diameter of the plasma generator 11 is 2.0        inches, the length of the plasma generator 11 (vertical in the        orientation depicted in FIG. 1 ) is 10.0 inches, the outside        diameter of the collar region 12 is 3.5 inches, the inside        diameter of the collar region 12 is 1.40 inches, the length of        the collar region 12 (vertical in the orientation depicted in        FIG. 1 ) is 3.0 inches, the diameter of the plume opening 22        (connection section between the plasma generator space 21 and        the collar space 23) is 1.38 inches, the reactant feed opening        24 is halfway along the length of the collar region 12, the        inside diameter of the first reactor section 13 is 8.0 inches,        the length of the first reactor section 13 (vertical in the        orientation depicted in FIG. 1 ) is 24 inches, the inside        diameter of the second reactor section 14 is 8.0 inches, the        length of the second reactor section 14 (vertical in the        orientation depicted in FIG. 1 ) is 24 inches (i.e., the first        reactor section 13 and the second reactor section 14 together        define a cylindrical chamber region of uniform diameter, which        is a combination of the first reaction chamber region 26 and the        second reaction chamber region 28, and that is 8 inches in        diameter and 48 inches in length), and the diameter of the        reactant feed opening 24 is 1/16 inch;    -   ionizing nitrogen and hydrogen in the plasma generator space 21        by supplying 35-45 kW to the electromagnetic wave generator 16;        and    -   supplying into the collar space (via the reactant feed opening        24, at a location at which the highest temperatures within the        apparatus 10 are) 20-90 mg/minute of solid elemental boron        powder (at room temperature before entering the apparatus 10)        entrained in nitrogen gas (e.g., 0.1 to 10.0 liters per minute),        while maintaining the pressure within the first reactor section        13 and the second reactor section 14 in the range of from 10 psi        to 20 psi (the pressure can fluctuate within this range).

In this representative embodiment, the temperature within at least partof the collar region 12 is about 8,000 K, the heat provided by theplasma, while temperatures in the first reactor section 13 and thesecond reactor section 14 are lower at farther distances from the collarregion 12.

The epitaxial h-BN/BNNT structures in accordance with the presentinventive subject matter resemble rock candy, in which (continuing withthe analogy) a boron nitride nanotube structure is the string, andnucleated and grown hexagonal boron nitride is the sugar.

Boron and nitrogen ions that are not transformed to boron nitridenanotube structures in the hottest zone of the apparatus aresupersaturated in the apparatus, and they build up on the boron nitridenanotube structures, where they nucleate hexagonal boron nitridestructures on boron nitride nanotube structures (i.e., making astructure having boron and nitrogen atoms nucleated on a boron nitridenanotube structure) and/or grow on previously nucleated boron nitridestructures.

Diameters of boron nitride nanotube structures formed in accordance withthe above representative embodiment are generally (e.g., 90% or more ofthem) in the range of from 3 to 30 nm.

Lengths of boron nitride nanotube structures formed in accordance withthe above representative embodiment are generally (e.g., 90% or more ofthem) in the range of from 10 nm to 50 micrometers.

Nodules of hexagonal boron nitride that is epitaxial with and coveringboron nitride nanotube structures formed in accordance with the aboverepresentative embodiment are generally (e.g., 90% or more of them) 1 nmto 200 nm thick (and are easy to identify, e.g., in TEM images).

Portions of boron nitride nanotube structures that are not covered byhexagonal boron nitride structures, and independent boron nitridenanotubes (if present), are very smooth and easy to identify (e.g., intransmission electron microscopy images (i.e., TEM images)).

Portions of residual boron (in products of the representative embodimentdescribed above) are generally amorphous (and are easy to identify,e.g., in TEM images). A representative product comprises 65 parts bymass of epitaxial h-BN/BNNT structures, and 35 parts by mass of residualboron and/or independent hexagonal boron nitride (typically includingless than 1 part by mass of independent hexagonal boron nitride).

Products in accordance with the present inventive subject matter exhibitnumerous properties that make them useful in a variety of applications.For example, epitaxial h-BN/BNNT structures are thicker thancorresponding independent boron nitride nanotubes, and/or have a morerough exterior, such that epitaxial h-BN/BNNT structures readily adhereto a matrix material, i.e., can provide physical/mechanical resistanceto removal from a matrix material (FIG. 3 is an illustration of anepitaxial h-BN/BNNT structure).

In addition, epitaxial h-BN/BNNT structures provide nano-nucleationsites for metals to crystallize (e.g., if casting metal, such asaluminum, magnesium or titanium, which have melting points that arelower than the temperature at which BNNT's degrade).

In addition, epitaxial h-BN/BNNT structures provide excellent propertiesafter being subjected to extremely high temperatures (in some cases,hexagonal boron nitride can act as a sacrificial layer for a boronnitride structure that it covers).

Some embodiments of epitaxial h-BN/BNNT structures in accordance withthe present inventive subject matter provide any combinations of theabove-described advantageous properties.

In general, increasing (i.e., above 4 weight percent) the proportion ofhydrogen in the mixture of nitrogen and hydrogen supplied into the port20 of the apparatus 10 increases the amount of epitaxial hexagonal boronnitride structures that are formed, and decreasing the proportion ofhydrogen (i.e., below 4 weight percent) in the mixture of nitrogen andhydrogen supplied into the port 20 of the apparatus 10 decreases theamount of epitaxial hexagonal boron nitride structures that are formed).While the present inventive subject matter is not limited to anyparticular theory, it is believed that the hydrogen supplied in themixture supplied into the port 20 provides energy that assists in thenucleation of hexagonal boron nitride structures on boron nitridenanotube structures.

Supplying solid elemental boron powder entrained in 0.1 to 10.0 litersper minute of nitrogen gas into the collar space via the reactant feedopening 24 (having a diameter of 1/16 inch) equates to a nitrogen gasflow rate of about 53.3 cm/sec-5,330 cm/sec. While the present inventivesubject matter is not limited to any particular theory, it is believedthat this high nitrogen gas flow rate causes a significant amount ofboron to pass unreacted through the region in which boron nitridenanotube structures are being formed, thereby providing boron that canbe involved in nucleating hexagonal boron nitride on the thus-formedboron nitride nanotube structures.

In the event that a larger apparatus were employed, the nitrogen gasflow rate in which the boron feed is entrained would be increased toadjust for the larger reaction zone through which hydrogen and boronwould pass through unreacted. Similarly, in the event that larger a flowrate of nitrogen and hydrogen is supplied to the plasma generator space21 (e.g., in a larger apparatus), the power supplied to theelectromagnetic wave generator 16 would be increased sufficiently toionize nitrogen and hydrogen.

While the present inventive subject matter is not limited to anyparticular theory, it is believed that the constriction of the reduceddiameter of the plume opening in creating flow characteristics that leadto production of epitaxial h-BN/BNNT structures. It is believed that thesmaller diameter in the collar space 23, in comparison to the largerdiameter in the first reaction chamber region 26, also contributes to(or provides) flow characteristics that leads to the production ofepitaxial h-BN/BNNT structures.

The above-described representative embodiment of a method also can beused to make compositions (or aggregates) that:

-   -   comprise a plurality of independent boron nitride nanotubes, in        which a sum of [1] a total mass of any independent hexagonal        boron nitride in the composition (or aggregate) and [2] a total        mass of any residual boron in the composition (or aggregate)        accounts for not more than 35% of the mass of the composition        (or aggregate), in accordance with the third aspect (or the        fourth aspect) of the present inventive subject matter;    -   comprise at least ten independent boron nitride nanotubes that        have a length of at least 50 nm, in which among a sum of [1] the        independent boron nitride nanotubes in the composition (or        aggregate) that have a length of at least 50 nm, and [2] boron        nitride nanotube structures in the composition (or aggregate)        that have a length of at least 50 nm, not more than 1% of said        sum have at least one defect selected from among dixie cup        defects and bamboo defects, in accordance with the fifth aspect        (or the sixth aspect) of the present inventive subject matter;        and/or    -   comprise at least ten independent boron nitride nanotubes, in        which among a sum of [1] the independent boron nitride nanotubes        in the composition (or aggregate) that have a length of at least        50 nm, and [2] boron nitride nanotube structures in the        composition (or aggregate) that have a length of at least 50 nm,        each of at least 50% of said sum is single-wall, in accordance        with the seventh aspect (or the eighth aspect) of the present        inventive subject matter.

Thus, in addition, the present inventive subject matter providescompositions (and aggregates):

-   -   that have advantageous high purity, e.g., in which a sum of [1]        a total mass of any independent hexagonal boron nitride in the        composition (or aggregate) and [2] a total mass of any residual        boron in the composition (or aggregate) accounts for not more        than 35% of the mass of the composition (or aggregate);    -   that have advantageous high quality, in which among a sum of [1]        the independent boron nitride nanotubes in the composition (or        aggregate) that have a length of at least 50 nm, and [2] boron        nitride nanotube structures in the composition (or aggregate)        that have a length of at least 50 nm, not more than 1% of said        sum have at least one defect selected from among dixie cup        defects and bamboo defects; and/or    -   that have an advantageously high percentage of independent boron        nitride nanotubes and boron nitride nanotube structures are        single-wall, e.g., in which among a sum of [1] the independent        boron nitride nanotubes in the composition (or aggregate) that        have a length of at least 50 nm, and [2] boron nitride nanotube        structures in the composition (or aggregate) that have a length        of at least 50 nm, each of at least 50% of said sum is        single-wall.

Such compositions or aggregates can have any combination of theabove-described advantageous characteristics, and can also have any ofthe above-described advantageous characteristics of epitaxial h-BN/BNNTstructures in accordance with the present inventive subject matter.

As noted above, in accordance with a ninth aspect of the presentinventive subject matter, there is provided a method of making acomposition, comprising:

-   -   supplying to a first region of a chamber a mixture of nitrogen        gas and hydrogen gas;    -   converting at least a portion of the mixture of nitrogen gas and        hydrogen gas to plasma;    -   supplying to a second region of the chamber a mixture of at        least one boron-containing material and nitrogen gas, whereby        the mixture of at least one boron-containing material and        nitrogen gas contacts the plasma to form a reaction mixture;    -   converting at least a portion of the mixture to epitaxial        h-BN/BNNT structures.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, the chamber comprises:

-   -   the first region;    -   the second region;    -   at least a third region;    -   a first connection section providing communication between the        first region and the second region; and    -   a second connection section providing communication between the        second region and the third region,    -   the first region having at least one first region        cross-sectional area perpendicular to an axis of the chamber,        the axis of the chamber extending through the first region, the        second region and the third region,    -   the second region having at least one second region        cross-sectional area perpendicular to the axis of the chamber,    -   the third region having at least one third region        cross-sectional area perpendicular to the axis of the chamber,    -   the first connection section having at least one first        connection section cross-sectional area perpendicular to the        axis of the chamber,    -   the second connection section having at least one second        connection section cross-sectional area perpendicular to the        axis of the chamber,    -   each first connection section cross-sectional area smaller than        the first region cross-sectional area and smaller than the        second region cross-sectional area,    -   each second connection section cross-sectional area smaller than        the third region cross-sectional area,

and in some of such embodiments:

-   -   pressure within at least a portion of the third region is at        least 10 psi;    -   pressure within at least a portion of the third region is in the        range of 10-20 psi; and/or    -   pressure within at least a portion of the third region is in the        range of 15-20 psi.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, the weight percentage ofhydrogen gas in the mixture of nitrogen gas and hydrogen gas is in therange of from 1 percent by mass to 7 percent by mass (in someembodiments at least 2 percent by mass, in some embodiments in the rangeof 2 percent by mass to 7 percent by mass, in some embodiments 4 percentby mass or about 4.0 percent by mass.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, the weight percentage ofhydrogen gas in the mixture of nitrogen gas and hydrogen gas is at least3 percent by mass.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, the weight percentage ofhydrogen gas in the mixture of nitrogen gas and hydrogen gas is at least4 percent by mass.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, the mixture of nitrogen gasand hydrogen gas is supplied to the first region in an amount of atleast 30 liters per minute.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, the mixture of nitrogen gasand hydrogen gas is supplied to the first region in an amount of atleast 40 liters per minute.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, the mixture of nitrogen gasand hydrogen gas is supplied to the first region in an amount of atleast 50 liters per minute.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, said supplying to a secondregion of the chamber of a mixture of at least one boron-containingmaterial and nitrogen gas comprises supplying boron at a rate of atleast 20 mg/minute.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, said supplying to a secondregion of the chamber of a mixture of at least one boron-containingmaterial and nitrogen gas comprises supplying boron at a rate in therange of from 20 mg/minute to 90 mg/minute.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, said supplying to a secondregion of the chamber of a mixture of at least one boron-containingmaterial and nitrogen gas comprises supplying nitrogen gas at a rate inthe range of from 0.1 liters per minute to 1.3 liters per minute.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, said supplying to a secondregion of the chamber of a mixture of at least one boron-containingmaterial and nitrogen gas comprises supplying nitrogen gas at a rate inthe range of from 1.3 liters per minute to 8.4 liters per minute.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, said converting at least aportion of the mixture of nitrogen gas and hydrogen gas to plasmacomprises generating electromagnetic waves within the first region.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, said generatingelectromagnetic waves comprises supplying radio frequency energy to anelectromagnetic wave generator at a power rate of at least 35 kW (and insome embodiments, 35-45 kW).

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, said generatingelectromagnetic waves comprises supplying radio frequency energy to anelectromagnetic wave generator at a power rate of at least 39 (and insome embodiments, 39-45 kW).

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, pressure within at least aportion of the chamber is at least 10 psi.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, pressure within at least aportion of the chamber is in the range of 10-20 psi.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, pressure within at least aportion of the chamber is in the range of 15-20 psi.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, the method further comprisescontacting at least some of the epitaxial h-BN/BNNT structures withnitric acid,

and in some of such embodiments, the method further comprises subjectingat least some of the epitaxial h-BN/BNNT structures to a temperature inthe range of from 700 to 900 degrees C.

In some embodiments according to the ninth aspect of the presentinventive subject matter, which can include or not include, as suitable,any of the other features described herein, the method further comprisessubjecting at least some of the epitaxial h-BN/BNNT structures to atemperature in the range of from 700 to 900 degrees C.

Example 1

50 liters per minute of a mixture of nitrogen and hydrogen (96 parts bymass nitrogen and 4 parts by mass hydrogen) was supplied into a plasmagenerator space of an apparatus as depicted in FIG. 1 (through theport). The apparatus further characterized in that the outside diameterof the plasma generator was 3.5 inches, the inside diameter of theplasma generator was 2.0 inches, the length of the plasma generator was10.0 inches, the outside diameter of the collar region was 3.5 inches,the inside diameter of the collar region was 1.40 inches, the length ofthe collar region was 3.0 inches, the diameter of the plume opening(connection section between the plasma generator space and the collarspace) was 1.38 inches, the reactant feed opening was halfway along thelength of the collar region, the inside diameter of the first reactorsection was 8.0 inches, the length of the first reactor section was 24inches, the inside diameter of the second reactor section was 8.0inches, the length of the second reactor section was 24 inches, and thediameter of the reactant feed opening was 1/16 inch;

39 kW was supplied to the electromagnetic wave generator to ionizenitrogen and hydrogen in the plasma generator space;

22 mg/minute of solid elemental boron powder (at room temperature beforeentering the apparatus) entrained in 1.3 liters per minute of nitrogengas was supplied into the collar space via the reactant feed opening;

the pressure within the first reactor section and the second reactorsection was maintained in the range of from 15 psi to 20 psi (i.e., thepressure fluctuated within this range), and the temperature within atleast part of the collar region was about 8,000 K.

FIG. 4 is a TEM image of a representative portion of the product ofExample 1, in which each of about 30% of the boron nitride nanotubestructures were at least 30% covered by epitaxial hexagonal boronnitride.

More than 50% of a sum of the independent boron nitride nanotubes andthe boron nitride nanotube structures were single-wall, with theremainder double-wall and multi-wall.

Less than 1% of a sum of the independent boron nitride nanotubes and theboron nitride nanotube structures had dixie cup defects or banboodefects.

A sum of the mass of residual boron and independent hexagonal boronnitride was less than 35% by mass of the product.

Example 2

50 liters per minute of a mixture of nitrogen and hydrogen (96 parts bymass nitrogen and 4 parts by mass hydrogen) was supplied (through theport) into a plasma generator space of the same apparatus that was usedin Example 1;

39 kW was supplied to the electromagnetic wave generator to ionizenitrogen and hydrogen in the plasma generator space;

22 mg/minute of solid elemental boron powder (at room temperature beforeentering the apparatus) entrained in 8.4 liters per minute of nitrogengas was supplied into the collar space via the reactant feed opening;

the pressure within the first reactor section and the second reactorsection was maintained in the range of from 15 psi to 20 psi (i.e., thepressure fluctuated within this range), and the temperature within atleast part of the collar region was about 8,000 K.

FIG. 5 is a TEM image of a representative portion of the product ofExample 2, in which each of about 90% of the boron nitride nanotubestructures were at least 30% covered by epitaxial hexagonal boronnitride.

FIG. 6 is a TEM image of a portion of the product of Example 2, theimage showing epitaxial h-BN/BNNT structures.

Reference number 61 points to an example of a high purity and highquality boron nitride nanotube in the TEM image of FIG. 6 .

Reference number 62 points to an example of unreacted amorphous boron inthe TEM image of FIG. 6 .

Reference numbers 63, 64 and 65 point to examples of epitaxial h-BN/BNNTstructures in the TEM image of FIG. 6 .

FIG. 7 is a TEM image of a portion of the product of Example 2, theimage showing an independent hexagonal boron nitride, epitaxialh-BN/BNNT structures (one of which comprises a clump of boron nitridenanotube structures).

Reference number 71 points to an example of an independent hexagonalboron nitride structure in the TEM image of FIG. 7 .

Reference number 72 points to an example of an epitaxial h-BN/BNNTstructure (comprising a clump of boron nitride nanotube structures) inthe TEM image of FIG. 7 .

Reference number 73 points to an example of an epitaxial h-BN/BNNTstructure (comprising a single boron nitride nanotube structure) in theTEM image of FIG. 7 .

Reference number 74 points to an example of an epitaxial h-BN/BNNTstructure (comprising a clump of two boron nitride nanotube structures)in the TEM image of FIG. 7 .

FIG. 8 is a TEM image of a portion of the product of Example 2, theimage showing a clump of boron nitride nanotube structures and epitaxialh-BN/BNNT structures.

Reference number 81 points to an example of an independent clump ofboron nitride nanotubes (i.e., a clump without epitaxial hexagonal boronnitride nucleation or growth) in the TEM image of FIG. 8 .

Reference number 82 points to an example of an epitaxial h-BN/BNNTstructure (comprising boron nitride nucleation on a side of a bundle ofboron nitride nanotube structures) in the TEM image of FIG. 8 .

FIG. 9 is a TEM image of a portion of the product of Example 2, theimage showing epitaxial h-BN/BNNT structures.

Reference number 91 points to an example of an epitaxial h-BN/BNNTstructure (comprising a single boron nitride nanotube structure) in theTEM image of FIG. 9 .

Reference number 92 points to an example of an epitaxial h-BN/BNNTstructure (comprising a clump of boron nitride nanotube structures) inthe TEM image of FIG. 9 .

FIG. 10 is a TEM image of a portion of the product of Example 2, theimage showing residual boron and epitaxial h-BN/BNNT structures.

Reference numbers 101 and 102 point to examples of residual amorphousboron in the TEM image of FIG. 10 .

Reference number 103 points to an example of an epitaxial h-BN/BNNTstructure in the TEM image of FIG. 10 .

Reference number 104 points to an example of an epitaxial h-BN/BNNTstructure (comprising a clump of boron nitride nanotube structures) inthe TEM image of FIG. 10 .

FIG. 11 is a TEM image of a portion of the product of Example 2, theimage showing residual boron and epitaxial h-BN/BNNT structures.

Reference numbers 111 and 112 point to examples of residual amorphousboron in the TEM image of FIG. 11 .

Reference numbers 113 and 114 point to examples of epitaxial h-BN/BNNTstructures in the TEM image of FIG. 11 .

FIG. 12 is a TEM image of a portion of the product of Example 2, theimage showing epitaxial h-BN/BNNT structures.

Reference numbers 121 and 122 point to examples of epitaxial h-BN/BNNTstructures in the TEM image of FIG. 12 .

More than 50% of a sum of the independent boron nitride nanotubes andthe boron nitride nanotube structures were single-wall, with theremainder double-wall and multi-wall.

Less than 1% of a sum of the independent boron nitride nanotubes and theboron nitride nanotube structures had dixie cup defects or banboodefects.

A sum of the mass of residual boron and independent hexagonal boronnitride was less than 35% by mass of the product.

FIG. 13 is a TEM image of an independent boron nitride nanotube.

Below are a series of numbered passages, each of which defines subjectmatter within the scope of the present inventive subject matter:

Passage 1. A composition comprising:

-   -   at least a first epitaxial h-BN/BNNT structure,    -   the first epitaxial h-BN/BNNT structure comprising at least a        first boron nitride nanotube structure and at least a first        hexagonal boron nitride structure,    -   the first hexagonal boron nitride structure epitaxial with        respect to the first boron nitride nanotube structure.

Passage 2. A composition as recited in passage 1, wherein:

-   -   a sum of [1] a quantity of independent boron nitride nanotubes        in the composition that have a length of at least 50 nm, and [2]        a quantity of boron nitride nanotube structures in the        composition that have a length of at least 50 nm, is at least        ten,    -   for each of a quantity of boron nitride nanotube structures that        is at least 10% of the sum of [1] the quantity of independent        boron nitride nanotubes in the composition that have a length of        at least 50 nm, and [2] the quantity of boron nitride nanotube        structures in the composition that have a length of at least 50        nm:        -   the boron nitride nanotube structure has a length of at            least 50 nm, and a total of at least 10% of the outermost            wall of the boron nitride nanotube structure is covered by            hexagonal boron nitride structures that are each epitaxial            with respect to the boron nitride nanotube structure.

Passage 3. A composition as recited in passage 2, wherein:

-   -   for each of a quantity of boron nitride nanotube structures that        is at least 30% of the sum of [1] the quantity of independent        boron nitride nanotubes in the composition that have a length of        at least 50 nm, and [2] the quantity of boron nitride nanotube        structures in the composition that have a length of at least 50        nm:        -   the boron nitride nanotube structure has a length of at            least 50 nm, and a total of at least 30% of the outermost            wall of the boron nitride nanotube structure is covered by            hexagonal boron nitride structures that are each epitaxial            with respect to the boron nitride nanotube structure.

Passage 4. A composition as recited in passage 2, wherein:

-   -   for each of a quantity of boron nitride nanotube structures that        is at least 80% of the sum of [1] the quantity of independent        boron nitride nanotubes in the composition that have a length of        at least 50 nm, and [2] the quantity of boron nitride nanotube        structures in the composition that have a length of at least 50        nm:        -   the boron nitride nanotube structure has a length of at            least 50 nm, and a total of at least 30% of the outermost            wall of the boron nitride nanotube structure is covered by            hexagonal boron nitride structures that are each epitaxial            with respect to the boron nitride nanotube structure.

Passage 5. A composition as recited in passage 1, wherein:

-   -   a sum of respective quantities of [1] independent boron nitride        nanotube clumps in the composition that have a length of at        least 50 nm, [2] boron nitride nanotube structure clumps in the        composition that have a length of at least 50 nm, [3] boron        nitride nanotube structure/independent boron nitride nanotube        clumps in the composition that have a length of at least 50 nm,        [4] independent boron nitride nanotubes in the composition that        are not in a clump and that have a length of at least 50 nm, and        [5] boron nitride nanotube structures in the composition that        are not in a clump and that have a length of at least 50 nm, is        at least ten,    -   for each of a quantity that is at least 30% of said sum, among        [2] the boron nitride nanotube structure clumps in the        composition that have a length of at least 50 nm, [3] the boron        nitride nanotube structure/independent boron nitride nanotube        clumps in the composition that have a length of at least 50 nm,        and [5] the boron nitride nanotube structures in the composition        that are not in a clump and that have a length of at least 50        nm:    -   a total of at least 10% of exterior atoms of [2] the boron        nitride nanotube structure clump, [3] the boron nitride nanotube        structure/independent boron nitride nanotube clump, or [5] the        boron nitride nanotube structure that is not in a clump,    -   is covered by hexagonal boron nitride structures that are each        epitaxial with respect to a boron nitride nanotube structure in        [2] the boron nitride nanotube structure clump, [3] the boron        nitride nanotube structure/independent boron nitride nanotube        clump, or [5] the boron nitride nanotube structure that is not        in a clump.

Passage 6. A composition as recited in passage 5, wherein:

-   -   for each of a quantity that is at least 30% of said sum, among        [2] the boron nitride nanotube structure clumps in the        composition that have a length of at least 50 nm, [3] the boron        nitride nanotube structure/independent boron nitride nanotube        clumps in the composition that have a length of at least 50 nm,        and [5] the boron nitride nanotube structures in the composition        that are not in a clump and that have a length of at least 50        nm:    -   a total of at least 30% of exterior atoms of [2] the boron        nitride nanotube structure clump, [3] the boron nitride nanotube        structure/independent boron nitride nanotube clump, or [5] the        boron nitride nanotube structure that is not in a clump,    -   is covered by hexagonal boron nitride structures that are each        epitaxial with respect to a boron nitride nanotube structure in        [2] the boron nitride nanotube structure clump, [3] the boron        nitride nanotube structure/independent boron nitride nanotube        clump, or [5] the boron nitride nanotube structure that is not        in a clump.

Passage 7. A composition as recited in passage 5, wherein:

-   -   for each of a quantity that is at least 80% of said sum, among        [2] the boron nitride nanotube structure clumps in the        composition that have a length of at least 50 nm, [3] the boron        nitride nanotube structure/independent boron nitride nanotube        clumps in the composition that have a length of at least 50 nm,        and [5] the boron nitride nanotube structures in the composition        that are not in a clump and that have a length of at least 50        nm:    -   a total of at least 30% of exterior atoms of [2] the boron        nitride nanotube structure clump, [3] the boron nitride nanotube        structure/independent boron nitride nanotube clump, or [5] the        boron nitride nanotube structure that is not in a clump,    -   is covered by hexagonal boron nitride structures that are each        epitaxial with respect to a boron nitride nanotube structure in        [2] the boron nitride nanotube structure clump, [3] the boron        nitride nanotube structure/independent boron nitride nanotube        clump, or [5] the boron nitride nanotube structure that is not        in a clump.

Passage 8. An aggregate comprising:

-   -   a one-piece structure comprising at least a first epitaxial        h-BN/BNNT structure,    -   the first epitaxial h-BN/BNNT structure comprising at least a        first boron nitride nanotube structure and at least a first        hexagonal boron nitride structure,    -   the first hexagonal boron nitride structure epitaxial with        respect to the boron nitride nanotube structure,    -   the one-piece structure having a first dimension of at least 100        nm and a second dimension of at least 100 nm, the second        dimension perpendicular to the first dimension.

Passage 9. An aggregate as recited in passage 8, wherein:

-   -   for each of a quantity of boron nitride nanotube structures in        the one-piece structure that is at least 10% of the sum of [1]        the quantity of independent boron nitride nanotubes in the        one-piece structure that have a length of at least 50 nm, and        [2] the quantity of boron nitride nanotube structures in the        one-piece structure that have a length of at least 50 nm:        -   a total of at least 10% of the outermost wall of the boron            nitride nanotube structure is covered by hexagonal boron            nitride structures that are each epitaxial with respect to            the boron nitride nanotube structure.

Passage 10. An aggregate as recited in passage 9, wherein: for each of aquantity of boron nitride nanotube structures in the one-piece structurethat is at least 30% of the sum of [1] the quantity of independent boronnitride nanotubes in the one-piece structure that have a length of atleast 50 nm, and [2] the quantity of boron nitride nanotube structuresin the one-piece structure that have a length of at least 50 nm:

-   -   a total of at least 30% of the outermost wall of the boron        nitride nanotube structure is covered by hexagonal boron nitride        structures that are each epitaxial with respect to the boron        nitride nanotube structure.

Passage 11. An aggregate as recited in passage 9, wherein: for each of aquantity of boron nitride nanotube structures in the one-piece structurethat is at least 80% of the sum of [1] the quantity of independent boronnitride nanotubes in the one-piece structure that have a length of atleast 50 nm, and [2] the quantity of boron nitride nanotube structuresin the one-piece structure that have a length of at least 50 nm:

-   -   a total of at least 30% of the outermost wall of the boron        nitride nanotube structure is covered by hexagonal boron nitride        structures that are each epitaxial with respect to the boron        nitride nanotube structure.

Passage 12. An aggregate as recited in passage 8, wherein:

-   -   for each of a quantity among [2] boron nitride nanotube        structure clumps in the one-piece structure that have a length        of at least 50 nm, [3] boron nitride nanotube        structure/independent boron nitride nanotube clumps in the        one-piece structure that have a length of at least 50 nm, and        [5] boron nitride nanotube structures in the one-piece structure    -   that are not in a clump and that have a length of at least 50        nm, that is at least 10% of a sum of respective quantities of        [1] independent boron nitride nanotube clumps in the one-piece        structure that have a length of at least 50 nm, [2] boron        nitride nanotube structure clumps in the one-piece structure        that have a length of at least 50 nm, [3] boron nitride nanotube        structure/independent boron nitride nanotube clumps in the        one-piece structure that have a length of at least 50 nm, [4]        independent boron nitride nanotubes in the one-piece structure        that are not in a clump and that have a length of at least 50        nm, and [5] boron nitride nanotube structures in the one-piece        structure that are not in a clump and that have a length of at        least 50 nm:        -   a total of at least 10% of exterior atoms of [2] the boron            nitride nanotube structure clump, [3] the boron nitride            nanotube structure/independent boron nitride nanotube clump,            or [5] the boron nitride nanotube structure that is not in a            clump,            -   is covered by hexagonal boron nitride structures that                are each epitaxial with respect to a boron nitride                nanotube structure in [2] the boron nitride nanotube                structure clump, [3] the boron nitride nanotube                structure/independent boron nitride nanotube clump, or                [5] the boron nitride nanotube structure that is not in                a clump.

Passage 13. An aggregate as recited in passage 12, wherein:

-   -   for each of a quantity among [2] boron nitride nanotube        structure clumps in the one-piece structure that have a length        of at least 50 nm, [3] boron nitride nanotube        structure/independent boron nitride nanotube clumps in the        one-piece structure that have a length of at least 50 nm, and        [5] boron nitride nanotube structures in the one-piece structure        that are not in a clump and that have a length of at least 50        nm,    -   that is at least 30% of a sum of respective quantities of [1]        independent boron nitride nanotube clumps in the one-piece        structure that have a length of at least 50 nm, [2] boron        nitride nanotube structure clumps in the one-piece structure        that have a length of at least 50 nm, [3] boron nitride nanotube        structure/independent boron nitride nanotube clumps in the        one-piece structure that have a length of at least 50 nm, [4]        independent boron nitride nanotubes in the one-piece structure        that are not in a clump and that have a length of at least 50        nm, and [5] boron nitride nanotube structures in the one-piece        structure that are not in a clump and that have a length of at        least 50 nm:        -   a total of at least 30% of exterior atoms of [2] the boron            nitride nanotube structure clump, [3] the boron nitride            nanotube structure/independent boron nitride nanotube clump,            or [5] the boron nitride nanotube structure that is not in a            clump,            -   is covered by hexagonal boron nitride structures that                are each epitaxial with respect to a boron nitride                nanotube structure in [2] the boron nitride nanotube                structure clump, [3] the boron nitride nanotube                structure/independent boron nitride nanotube clump, or                [5] the boron nitride nanotube structure that is not in                a clump.

Passage 14. An aggregate as recited in passage 12, wherein:

-   -   for each of a quantity among [2] boron nitride nanotube        structure clumps in the one-piece structure that have a length        of at least 50 nm, [3] boron nitride nanotube        structure/independent boron nitride nanotube clumps in the        one-piece structure that have a length of at least 50 nm, and        [5] boron nitride nanotube structures in the one-piece structure        that are not in a clump and that have a length of at least 50        nm,    -   that is at least 80% of a sum of respective quantities of [1]        independent boron nitride nanotube clumps in the one-piece        structure that have a length of at least 50 nm, [2] boron        nitride nanotube structure clumps in the one-piece structure        that have a length of at least 50 nm, [3] boron nitride nanotube        structure/independent boron nitride nanotube clumps in the        one-piece structure that have a length of at least 50 nm, [4]        independent boron nitride nanotubes in the one-piece structure        that are not in a clump and that have a length of at least 50        nm, and [5] boron nitride nanotube structures in the one-piece        structure that are not in a clump and that have a length of at        least 50 nm:        -   a total of at least 30% of exterior atoms of [2] the boron            nitride nanotube structure clump, [3] the boron nitride            nanotube structure/independent boron nitride nanotube clump,            or [5] the boron nitride nanotube structure that is not in a            clump,            -   is covered by hexagonal boron nitride structures that                are each epitaxial with respect to a boron nitride                nanotube structure in [2] the boron nitride nanotube                structure clump, [3] the boron nitride nanotube                structure/independent boron nitride nanotube clump, or                [5] the boron nitride nanotube structure that is not in                a clump.

Passage 15. A composition, comprising:

-   -   a plurality of independent boron nitride nanotubes,    -   a sum of [1] a total mass of any independent hexagonal boron        nitride in the composition and [2] a total mass of any residual        boron in the composition accounts for not more than 35% of the        mass of the composition.

Passage 16. A composition as recited in passage 15, wherein a sum of [1]the total mass of any independent hexagonal boron nitride in thecomposition and [2] the total mass of any residual boron in thecomposition accounts for not more than 25% of the mass of thecomposition.

Passage 17. An aggregate, comprising:

-   -   a one-piece structure comprising a plurality of independent        boron nitride nanotubes,    -   the one-piece structure having a first dimension of at least 100        nm and a second dimension of at least 100 nm, the second        dimension perpendicular to the first dimension,    -   a sum of [1] a total mass of independent hexagonal boron nitride        in the one-piece structure and [2] a total mass of any residual        boron in the one-piece structure accounts for not more than 35%        of the mass of the one-piece structure.

Passage 18. An aggregate as recited in passage 17, wherein a sum of [1]the total mass of any independent hexagonal boron nitride in theaggregate and [2] the total mass of any residual boron in the aggregateaccounts for not more than 25% of the mass of the aggregate.

Passage 19. A composition, comprising:

-   -   at least ten independent boron nitride nanotubes that have a        length of at least 50 nm,    -   among a sum of [1] the independent boron nitride nanotubes in        the composition that have a length of at least 50 nm, and [2]        boron nitride nanotube structures in the composition that have a        length of at least 50 nm, not more than 1% of said sum have at        least one defect selected from among dixie cup defects and        bamboo defects.

Passage 20. An aggregate, comprising:

-   -   a one-piece structure comprising a plurality of independent        boron nitride nanotubes,    -   the one-piece structure having a first dimension of at least 100        nm and a second dimension of at least 100 nm, the second        dimension perpendicular to the first dimension,    -   among a sum of [1] the independent boron nitride nanotubes in        the one-piece structure that have a length of at least 50 nm,        and [2] boron nitride nanotube structures in the one-piece        structure that have a length of at least 50 nm, not more than 1%        of said sum have at least one defect selected from among dixie        cup defects and bamboo defects.

Passage 21. A composition, comprising:

-   -   at least ten independent boron nitride nanotubes,    -   among a sum of [1] the independent boron nitride nanotubes in        the composition that have a length of at least 50 nm, and [2]        boron nitride nanotube structures in the composition that have a        length of at least 50 nm, each of at least 50% of said sum is        single-wall.

Passage 22. A composition as recited in passage 21, wherein each of atleast some of said sum of [1] the independent boron nitride nanotubes inthe composition that have a length of at least 50 nm, and [2] the boronnitride nanotube structures in the composition that have a length of atleast 50 nm, that is single-wall is in an independent boron nitridenanotube clump, a boron nitride nanotube structure clump, or a boronnitride nanotube structure/independent boron nitride nanotube clump.

Passage 23. A composition as recited in passage 21, wherein among a sumof [1] the independent boron nitride nanotubes in the composition thathave a length of at least 50 nm, and [2] boron nitride nanotubestructures in the composition that have a length of at least 50 nm, eachof 50-60 percent of said sum is single-wall.

Passage 24. An aggregate, comprising:

-   -   a one-piece structure comprising at least one independent boron        nitride nanotube,    -   the one-piece structure having a first dimension of at least 100        nm and a second dimension of at least 100 nm, the second        dimension perpendicular to the first dimension,    -   among a sum of [1] the independent boron nitride nanotubes in        the one-piece structure that have a length of at least 50 nm,        and [2] boron nitride nanotube structures in the one-piece        structure that have a length of at least 50 nm, each of at least        50% of said sum is single-wall.

Passage 25. An aggregate as recited in passage 24, wherein each of atleast some of said sum of [1] the independent boron nitride nanotubes inthe one-piece structure that have a length of at least 50 nm, and [2]the boron nitride nanotube structures in the one-piece structure thathave a length of at least 50 nm, that is single-wall is in anindependent boron nitride nanotube clump, a boron nitride nanotubestructure clump, or a boron nitride nanotube structure/independent boronnitride nanotube clump.

Passage 26. An aggregate as recited in passage 24, wherein among a sumof [1] the independent boron nitride nanotubes in the one-piecestructure that have a length of at least 50 nm, and [2] boron nitridenanotube structures in the one-piece structure that have a length of atleast 50 nm, each of 50-60 percent of said sum is single-wall.

Passage 27. A composition as recited in any one of passages 1-7, 19 and21, wherein a combined mass of the epitaxial h-BN/BNNT structures in thecomposition accounts for at least 65% of the mass of the composition.

Passage 28. A composition as recited in passage 27, wherein the combinedmass of the epitaxial h-BN/BNNT structures in the composition accountsfor at least 75% of the mass of the composition.

Passage 29. An aggregate as recited in any one of passages 8-14, 20 and24, wherein a combined mass of the epitaxial h-BN/BNNT structures in thecomposition accounts for at least 65% of the mass of the one-piecestructure.

Passage 30. An aggregate as recited in passage 29, wherein the combinedmass of the epitaxial h-BN/BNNT structures in the composition accountsfor at least 75% of the mass of the one-piece structure.

Passage 31. A composition as recited in any one of passages 1-7, 15, 16,19, 21-23, 27 and 28, wherein at least 10% by mass of the compositioncomprises hexagonal boron nitride structures that are each epitaxialwith respect to a boron nitride nanotube structure.

Passage 32. An aggregate as recited in any one of passages 8-14, 17, 18,20, 24-26, 29 and 30, wherein at least 10% by mass of the one-piecestructure comprises hexagonal boron nitride structures that are eachepitaxial with respect to a boron nitride nanotube structure.

Passage 33. A composition as recited in any one of passages 1-7, 15, 16,19, 21-23, 27, 28 and 31, wherein for each of at least 10% of the atomsin the composition, the atom is in a hexagonal boron nitride structurethat is epitaxial with a boron nitride nanotube structure in thecomposition.

Passage 34. An aggregate as recited in any one of passages 8-14, 17, 18,20, 24-26, 29, 30 and 32, wherein for each of at least 10% of the atomsin the one-piece structure, the atom is in a hexagonal boron nitridestructure that is epitaxial with a boron nitride nanotube structure inthe composition.

Passage 35. A composition as recited in any one of passages 1-7, 27, 28,31 and 33, wherein the sum of [1] a combined mass of any independenthexagonal boron nitride in the composition and [2] a combined mass ofany amorphous boron in the composition accounts for less than 35% of themass of the composition.

Passage 36. An aggregate as recited in any one of passages 8-14, 29, 30,32 and 34, wherein the sum of [1] a combined mass of any independenthexagonal boron nitride in the one-piece structure and [2] a combinedmass of any amorphous boron in the one-piece structure accounts for lessthan 35% of the mass of the one-piece structure.

Passage 37. A composition as recited in any one of passages 1-7, 15, 16,27, 28, 31, 33 and 35, wherein among a sum of [1] the independent boronnitride nanotubes in the composition that have a length of at least 50nm, and [2] boron nitride nanotube structures in the composition thathave a length of at least 50 nm, not more than 1% of said sum have atleast one defect selected from among dixie cup defects and bamboodefects.

Passage 38. An aggregate as recited in any one of passages 8-14, 17, 18,29, 30, 32, 34 and 36, wherein among a sum of [1] the independent boronnitride nanotubes in the one-piece structure that have a length of atleast 50 nm, and [2] boron nitride nanotube structures in the one-piecestructure that have a length of at least 50 nm, not more than 1% of saidsum have at least one defect selected from among dixie cup defects andbamboo defects.

Passage 39. A composition as recited in any one of passages 1-7, 15, 16,19, 27, 28, 31, 33, 35 and 37, wherein among a sum of [1] theindependent boron nitride nanotubes in the composition that have alength of at least 50 nm, and [2] boron nitride nanotube structures inthe composition that have a length of at least 50 nm, each of at least50% of said sum is single-wall.

Passage 40. An aggregate as recited in any one of passages 8-14, 17, 18,20, 29, 30, 32, 34, 36 and 38, wherein among a sum of [1] theindependent boron nitride nanotubes in the one-piece structure that havea length of at least 50 nm, and [2] boron nitride nanotube structures inthe one-piece structure that have a length of at least 50 nm, each of atleast 50% of said sum is single-wall.

Passage 41. A composition as recited in any one of passages 15, 16, 27,28, 31, 33, 35, 37 and 39, wherein independent hexagonal boron nitrideaccounts for not more than 1 percent by mass of the composition.

Passage 42. An aggregate as recited in any one of passages 17, 18, 29,30, 32, 34, 36, 38 and 40, wherein independent hexagonal boron nitrideaccounts for not more than 1 percent by mass of the aggregate.

Passage 43. A method of making a composition, comprising:

-   -   supplying to a first region of a chamber a mixture of nitrogen        gas and hydrogen gas;    -   converting at least a portion of the mixture of nitrogen gas and        hydrogen gas to plasma;    -   supplying to a second region of the chamber a mixture of at        least one boron-containing material and nitrogen gas, whereby        the mixture of at least one boron-containing material and        nitrogen gas contacts the plasma to form a reaction mixture;    -   converting at least a portion of the mixture to epitaxial        h-BN/BNNT structures.

Passage 44. A method as recited in passage 43, wherein the chambercomprises:

-   -   the first region;    -   the second region;    -   at least a third region;    -   a first connection section providing communication between the        first region and the second region; and    -   a second connection section providing communication between the        second region and the third region,    -   the first region having at least one first region        cross-sectional area perpendicular to an axis of the chamber,        the axis of the chamber extending through the first region, the        second region and the third region,    -   the second region having at least one second region        cross-sectional area perpendicular to the axis of the chamber,    -   the third region having at least one third region        cross-sectional area perpendicular to the axis of the chamber,    -   the first connection section having at least one first        connection section cross-sectional area perpendicular to the        axis of the chamber,    -   the second connection section having at least one second        connection section cross-sectional area perpendicular to the        axis of the chamber,    -   each first connection section cross-sectional area smaller than        the first region cross-sectional area and smaller than the        second region cross-sectional area,    -   each second connection section cross-sectional area smaller than        the third region cross-sectional area.

Passage 45. A method as recited in passage 44, wherein pressure withinat least a portion of the third region is at least 10 psi.

Passage 46. A method as recited in passage 44, wherein pressure withinat least a portion of the third region is in the range of 10-20 psi.

Passage 47. A method as recited in passage 44, wherein pressure withinat least a portion of the third region is in the range of 15-20 psi.

Passage 48. A method as recited in any one of passages 43-47, whereinthe weight percentage of hydrogen gas in the mixture of nitrogen gas andhydrogen gas is at least 2 percent by mass.

Passage 49. A method as recited in any one of passages 43-47, whereinthe weight percentage of hydrogen gas in the mixture of nitrogen gas andhydrogen gas is at least 3 percent by mass.

Passage 50. A method as recited in any one of passages 43-47, whereinthe weight percentage of hydrogen gas in the mixture of nitrogen gas andhydrogen gas is at least 4 percent by mass.

Passage 51. A method as recited in any one of passages 43-50, whereinthe mixture of nitrogen gas and hydrogen gas is supplied to the firstregion in an amount of at least 30 liters per minute.

Passage 52. A method as recited in any one of passages 43-50, whereinthe mixture of nitrogen gas and hydrogen gas is supplied to the firstregion in an amount of at least 40 liters per minute.

Passage 53. A method as recited in any one of passages 43-50, whereinthe mixture of nitrogen gas and hydrogen gas is supplied to the firstregion in an amount of at least 50 liters per minute.

Passage 54. A method as recited in any one of passages 43-53, whereinsaid supplying to a second region of the chamber of a mixture of atleast one boron-containing material and nitrogen gas comprises supplyingboron at a rate of at least 20 mg/minute.

Passage 55. A method as recited in any one of passages 43-53, whereinsaid supplying to a second region of the chamber of a mixture of atleast one boron-containing material and nitrogen gas comprises supplyingboron at a rate in the range of from 20 mg/minute to 90 mg/minute.

Passage 56. A method as recited in any one of passages 43-55, whereinsaid supplying to a second region of the chamber of a mixture of atleast one boron-containing material and nitrogen gas comprises supplyingnitrogen gas at a rate in the range of from 0.1 liters per minute to 1.3liters per minute.

Passage 57. A method as recited in any one of passages 43-55, whereinsaid supplying to a second region of the chamber of a mixture of atleast one boron-containing material and nitrogen gas comprises supplyingnitrogen gas at a rate in the range of from 1.3 liters per minute to 8.4liters per minute.

Passage 58. A method as recited in any one of passages 43-57, whereinsaid converting at least a portion of the mixture of nitrogen gas andhydrogen gas to plasma comprises generating electromagnetic waves withinthe first region.

Passage 59. A method as recited in passage 58, wherein said generatingelectromagnetic waves comprises supplying radio frequency energy to anelectromagnetic wave generator at a power rate of at least 35 kW.

Passage 60. A method as recited in passage 58, wherein said generatingelectromagnetic waves comprises supplying radio frequency energy to anelectromagnetic wave generator at a power rate of at least 39 kW.

Passage 61. A method as recited in any one of passages 43-60, whereinthe method further comprises contacting at least some of the epitaxialh-BN/BNNT structures with nitric acid.

Passage 62. A method as recited in any one of passages 43-61, whereinthe method further comprises subjecting at least some of the epitaxialh-BN/BNNT structures to a temperature in the range of from 700 to 900degrees C.

The invention claimed is:
 1. A composition comprising: at least a firsth-BN/BNNT structure, the first h-BN/BNNT structure comprising at least afirst boron nitride nanotube structure and at least a first hexagonalboron nitride structure, wherein: a sum of [1] a quantity of independentboron nitride nanotubes in the composition that have a length of atleast 50 nm, and [2] a quantity of boron nitride nanotube structures inthe composition that have a length of at least 50 nm, is at least ten,for each of a quantity of boron nitride nanotube structures that is atleast 10% of the sum of [1] the quantity of independent boron nitridenanotubes in the composition that have a length of at least 50 nm, and[2] the quantity of boron nitride nanotube structures in the compositionthat have a length of at least 50 nm: the boron nitride nanotubestructure has a length of at least 50 nm, and a total of at least 10% ofthe outermost wall of the boron nitride nanotube structure is covered byhexagonal boron nitride structures.
 2. A composition as recited in claim1, wherein: for each of a quantity of boron nitride nanotube structuresthat is at least 30% of the sum of [1] the quantity of independent boronnitride nanotubes in the composition that have a length of at least 50nm, and [2] the quantity of boron nitride nanotube structures in thecomposition that have a length of at least 50 nm: the boron nitridenanotube structure has a length of at least 50 nm, and a total of atleast 30% of the outermost wall of the boron nitride nanotube structureis covered by hexagonal boron nitride structures.
 3. A composition asrecited in claim 1, wherein: for each of a quantity of boron nitridenanotube structures that is at least 80% of the sum of [1] the quantityof independent boron nitride nanotubes in the composition that have alength of at least 50 nm, and [2] the quantity of boron nitride nanotubestructures in the composition that have a length of at least 50 nm: theboron nitride nanotube structure has a length of at least 50 nm, and atotal of at least 30% of the outermost wall of the boron nitridenanotube structure is covered by hexagonal boron nitride structures. 4.A composition as recited in claim 1, wherein: a sum of respectivequantities of [1] independent boron nitride nanotube clumps in thecomposition that have a length of at least 50 nm, [2] boron nitridenanotube structure clumps in the composition that have a length of atleast 50 nm, [3] boron nitride nanotube structure/independent boronnitride nanotube clumps in the composition that have a length of atleast 50 nm, [4] independent boron nitride nanotubes in the compositionthat are not in a clump and that have a length of at least 50 nm, and[5] boron nitride nanotube structures in the composition that are not ina clump and that have a length of at least 50 nm, is at least ten, foreach of a quantity that is at least 30% of said sum, among [2] the boronnitride nanotube structure clumps in the composition that have a lengthof at least 50 nm, [3] the boron nitride nanotube structure/independentboron nitride nanotube clumps in the composition that have a length ofat least 50 nm, and [5] the boron nitride nanotube structures in thecomposition that are not in a clump and that have a length of at least50 nm: a total of at least 10% of exterior atoms of [2] the boronnitride nanotube structure clump, [3] the boron nitride nanotubestructure/independent boron nitride nanotube clump, or [5] the boronnitride nanotube structure that is not in a clump, is covered byhexagonal boron nitride structures.
 5. An aggregate comprising: aone-piece structure comprising a composition comprising at least a firsth-BN/BNNT structure as recited in claim 1, the one-piece structurehaving a first dimension of at least 100 nm and a second dimension of atleast 100 nm, the second dimension perpendicular to the first dimension.6. An aggregate as recited in claim 5, wherein: for each of a quantityamong [2] boron nitride nanotube structure clumps in the one-piecestructure that have a length of at least 50 nm, [3] boron nitridenanotube structure/independent boron nitride nanotube clumps in theone-piece structure that have a length of at least 50 nm, and [5] boronnitride nanotube structures in the one-piece structure that are not in aclump and that have a length of at least 50 nm, that is at least 10% ofa sum of respective quantities of [1] independent boron nitride nanotubeclumps in the one-piece structure that have a length of at least 50 nm,[2] boron nitride nanotube structure clumps in the one-piece structurethat have a length of at least 50 nm, [3] boron nitride nanotubestructure/independent boron nitride nanotube clumps in the one-piecestructure that have a length of at least 50 nm, [4] independent boronnitride nanotubes in the one-piece structure that are not in a clump andthat have a length of at least 50 nm, and [5] boron nitride nanotubestructures in the one-piece structure that are not in a clump and thathave a length of at least 50 nm: a total of at least 10% of exterioratoms of [2] the boron nitride nanotube structure clump, [3] the boronnitride nanotube structure/independent boron nitride nanotube clump, or[5] the boron nitride nanotube structure that is not in a clump, iscovered by hexagonal boron nitride structures in [2] the boron nitridenanotube structure clump, [3] the boron nitride nanotubestructure/independent boron nitride nanotube clump, or [5] the boronnitride nanotube structure that is not in a clump.
 7. A compositioncomprising: at least a first epitaxial h-BN/BNNT structure; and at leastone metal, the first epitaxial h-BN/BNNT structure comprising at least afirst boron nitride nanotube structure and at least a first hexagonalboron nitride structure, the first hexagonal boron nitride structureepitaxial with respect to the first boron nitride nanotube structure,wherein atoms in the first hexagonal boron nitride structure areepitaxially aligned with the atoms in the first boron nitride nanotubestructure that are closest to the first hexagonal boron nitridestructure, the at least one metal adhered to the first epitaxialh-BN/BNNT structure.
 8. A composition as recited in claim 7, wherein theat least one metal comprises at least one atom selected from aluminum,magnesium and titanium.
 9. A composition as recited in claim 7, wherein:a sum of [1] a quantity of independent boron nitride nanotubes in thecomposition that have a length of at least 50 nm, and [2] a quantity ofboron nitride nanotube structures in the composition that have a lengthof at least 50 nm, is at least ten, for each of a quantity of boronnitride nanotube structures that is at least 10% of the sum of [1] thequantity of independent boron nitride nanotubes in the composition thathave a length of at least 50 nm, and [2] the quantity of boron nitridenanotube structures in the composition that have a length of at least 50nm: the boron nitride nanotube structure has a length of at least 50 nm,and a total of at least 10% of the outermost wall of the boron nitridenanotube structure is covered by hexagonal boron nitride structures thatare each epitaxial with respect to the boron nitride nanotube structure.10. A composition as recited in claim 7, wherein: a sum of [1] aquantity of independent boron nitride nanotubes in the composition thathave a length of at least 50 nm, and [2] a quantity of boron nitridenanotube structures in the composition that have a length of at least 50nm, is at least ten, for each of a quantity of boron nitride nanotubestructures that is at least 30% of the sum of [1] the quantity ofindependent boron nitride nanotubes in the composition that have alength of at least 50 nm, and [2] the quantity of boron nitride nanotubestructures in the composition that have a length of at least 50 nm: theboron nitride nanotube structure has a length of at least 50 nm, and atotal of at least 30% of the outermost wall of the boron nitridenanotube structure is covered by hexagonal boron nitride structures thatare each epitaxial with respect to the boron nitride nanotube structure.11. A composition as recited in claim 7, wherein: a sum of respectivequantities of [1] independent boron nitride nanotube clumps in thecomposition that have a length of at least 50 nm, [2] boron nitridenanotube structure clumps in the composition that have a length of atleast 50 nm, [3] boron nitride nanotube structure/independent boronnitride nanotube clumps in the composition that have a length of atleast 50 nm, [4] independent boron nitride nanotubes in the compositionthat are not in a clump and that have a length of at least 50 nm, and[5] boron nitride nanotube structures in the composition that are not ina clump and that have a length of at least 50 nm, is at least ten, foreach of a quantity that is at least 30% of said sum, among [2] the boronnitride nanotube structure clumps in the composition that have a lengthof at least 50 nm, [3] the boron nitride nanotube structure/independentboron nitride nanotube clumps in the composition that have a length ofat least 50 nm, and [5] the boron nitride nanotube structures in thecomposition that are not in a clump and that have a length of at least50 nm: a total of at least 10% of exterior atoms of [2] the boronnitride nanotube structure clump, [3] the boron nitride nanotubestructure/independent boron nitride nanotube clump, or [5] the boronnitride nanotube structure that is not in a clump, is covered byhexagonal boron nitride structures that are each epitaxial with respectto a boron nitride nanotube structure in [2] the boron nitride nanotubestructure clump, [3] the boron nitride nanotube structure/independentboron nitride nanotube clump, or [5] the boron nitride nanotubestructure that is not in a clump.
 12. An aggregate comprising: acomposition comprising at least a first one-piece structure comprising acomposition comprising least a first epitaxial h-BN/BNNT structure asrecited in claim 7, the one-piece structure having a first dimension ofat least 100 nm and a second dimension of at least 100 nm, the seconddimension perpendicular to the first dimension.
 13. An aggregate asrecited in claim 12, wherein: for each of a quantity among [2] boronnitride nanotube structure clumps in the one-piece structure that have alength of at least 50 nm, [3] boron nitride nanotubestructure/independent boron nitride nanotube clumps in the one-piecestructure that have a length of at least 50 run, and [5] boron nitridenanotube structures in the one-piece structure that are not in a clumpand that have a length of at least 50 nm, that is at least 10% of a sumof respective quantities of [1] independent boron nitride nanotubeclumps in the one-piece structure that have a length of at least 50 nm,[2]boron nitride nanotube structure clumps in the one-piece structurethat have a length of at least 50 nm, [3] boron nitride nanotubestructure/independent boron nitride nanotube clumps in the one-piecestructure that have a length of at least 50 nm, [4] independent boronnitride nanotubes in the one-piece structure that are not in a clump andthat have a length of at least 50 nm, and [5] boron nitride nanotubestructures in the one-piece structure that are not in a clump and thathave a length of at least 50 nm: a total of at least 10% of exterioratoms of [2] the boron nitride nanotube structure clump, [3] the boronnitride nanotube structure/independent boron nitride nanotube clump, or[5] the boron nitride nanotube structure that is not in a clump, iscovered by hexagonal boron nitride structures in [2] the boron nitridenanotube structure clump, [3] the boron nitride nanotubestructure/independent boron nitride nanotube clump, or [5] the boronnitride nanotube structure that is not in a clump.
 14. A composition,comprising: a plurality of independent boron nitride nanotubes, a sum of[1] a total mass of any independent hexagonal boron nitride in thecomposition and [2] a total mass of any residual boron in thecomposition accounts for not more than 35% of the mass of thecomposition.
 15. A composition as recited in claim 14, whereinindependent hexagonal boron nitride accounts for not more than 1 percentby mass of the composition.
 16. A composition as recited in claim 14,wherein a sum of [1] the total mass of any independent hexagonal boronnitride in the composition and [2] the total mass of any residual boronin the composition, accounts for not more than 25% of the mass of thecomposition.
 17. A material comprising at least a first hexagonal boronnitride structure and at least a first boron nitride nanotube structure,wherein atoms in the first hexagonal boron nitride structure areepitaxially aligned with atoms in the first boron nitride nanotubestructure that are closest to the first hexagonal boron nitridestructure.
 18. A composition as recited in claim 17, wherein: a sum of[1] a quantity of independent boron nitride nanotubes in the compositionthat have a length of at least 50 nm, and [2] a quantity of boronnitride nanotube structures in the composition that have a length of atleast 50 nm, is at least ten, for each of a quantity of boron nitridenanotube structures that is at least 10% of the sum of [1] the quantityof independent boron nitride nanotubes in the composition that have alength of at least 50 nm, and [2] the quantity of boron nitride nanotubestructures in the composition that have a length of at least 50 nm: theboron nitride nanotube structure has a length of at least 50 nm, and atotal of at least 10% of the outermost wall of the boron nitridenanotube structure is covered by hexagonal boron nitride structures thatare each epitaxial with respect to the boron nitride nanotube structure.19. A composition as recited in claim 17, wherein: a sum of [1] aquantity of independent boron nitride nanotubes in the composition thathave a length of at least 50 nm, and [2] a quantity of boron nitridenanotube structures in the composition that have a length of at least 50nm, is at least ten, for each of a quantity of boron nitride nanotubestructures that is at least 30% of the sum of [1] the quantity ofindependent boron nitride nanotubes in the composition that have alength of at least 50 nm, and [2] the quantity of boron nitride nanotubestructures in the composition that have a length of at least 50 nm: theboron nitride nanotube structure has a length of at least 50 nm, and atotal of at least 30% of the outermost wall of the boron nitridenanotube structure is covered by hexagonal boron nitride structures thatare each epitaxial with respect to the boron nitride nanotube structure.20. A composition as recited in claim 17, wherein: a sum of respectivequantities of [1] independent boron nitride nanotube clumps in thecomposition that have a length of at least 50 nm, [2] boron nitridenanotube structure clumps in the composition that have a length of atleast 50 nm, [3] boron nitride nanotube structure/independent boronnitride nanotube clumps in the composition that have a length of atleast 50 nm, [4] independent boron nitride nanotubes in the compositionthat are not in a clump and that have a length of at least 50 nm, and[5] boron nitride nanotube structures in the composition that are not ina clump and that have a length of at least 50 nm, is at least ten, foreach of a quantity that is at least 30% of said sum, among [2] the boronnitride nanotube structure clumps in the composition that have a lengthof at least 50 nm, [3] the boron nitride nanotube structure/independentboron nitride nanotube clumps in the composition that have a length ofat least 50 nm, and [5] the boron nitride nanotube structures in thecomposition that are not in a clump and that have a length of at least50 nm: a total of at least 10% of exterior atoms of [2] the boronnitride nanotube structure clump, [3] the boron nitride nanotubestructure/independent boron nitride nanotube clump, or [5] the boronnitride nanotube structure that is not in a clump, is covered byhexagonal boron nitride structures that are each epitaxial with respectto a boron nitride nanotube structure in [2] the boron nitride nanotubestructure clump, [3] the boron nitride nanotube structure/independentboron nitride nanotube clump, or [5] the boron nitride nanotubestructure that is not in a clump.